JP2002202599A - Composite patterning layer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite patterning layer excellent in photo-curability, ensuring a large curing depth even when an inorganic fine powder is contained in very large quantities, excellent in shelf stability, having stable adhesion to a substrate in each of drying, exposing, developing and baking steps, excellent also in developability and development resistance to an alkali developing solution, suitability to baking, etc., and capable of giving a high definition pattern having a high aspect ratio and to provide a method for producing the composite patterning layer. SOLUTION: The composite patterning layer is formed from (A) an acid- containing alkali developable photosensitive resin composition and (B) a photosensitive resin composition containing a photo-curable resin which is made alkali-soluble by acid decomposition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite pattern layer and a method of manufacturing the same, and particularly proposes a configuration of a pattern layer effective for forming electrodes of a plasma display panel.

[0002]

2. Description of the Related Art Conventionally, formation of a conductor pattern or a dielectric pattern in a plasma display panel or the like has been performed.
A pattern has been formed by a screen printing method using a conductive paste containing metal powder or a glass paste containing glass powder. However, in pattern formation by this screen printing method, skill is required, and there are problems such as rubbing and bleeding at the time of printing, a decrease in alignment accuracy due to expansion and contraction of the screen, jaggies of screen mesh marks, and the yield is low. However, it is becoming difficult to cope with high-definition patterns and enlargement. Therefore, development of a pattern processing material and a pattern forming technique capable of more stably responding to a demand for a high-definition pattern and a large size is desired.

On the other hand, a photolithography method has been proposed as a pattern forming technique instead of the screen printing method (for example, Japanese Patent Application Laid-Open No. 1-296534,
JP-A-2-165538, JP-A-5-34299
No. 2). The photolithography method is a technique in which an ultraviolet-curable glass paste material is coated on an insulating substrate, and a desired pattern is formed by exposure and development.

[0004] In this photolithography method, an alkali developing type paste material containing a polymer compound having a carboxyl group as a resin component is widely used, particularly in consideration of the environment and the like. However, when basic inorganic fine particles such as glass frit are blended with the polymer compound having a carboxyl group and used, the viscosity stability of the obtained paste is extremely poor, and the paste work is caused by gelation or reduced fluidity. However, there is a limit to the high definition of the formed pattern because of the deterioration of the properties and the decrease in the developability of the dried coating film. In addition, this alkali-developing type paste material contains a combination of an alkali-soluble binder and a photocurable component, and a portion that is cured by irradiation (exposure) of active energy rays such as ultraviolet rays also has a group showing solubility in alkali. Exists. For this reason, there is a problem that the so-called undercut phenomenon is apt to occur, in that the surface and the deep portion cured by light are also eroded by the alkali developing solution. In other words, the difference in alkali solubility between the exposed and unexposed areas was not sufficient, so that not only the setting of the developing time was narrow, but also the high definition was limited.

On the other hand, in order to increase the difference in alkali solubility between the exposed and unexposed areas, a binder in which a carboxyl group is blocked in advance is used. There are ways to make sex differences. However, in this method, although a photoacid generator or a thermal acid generator can be used as a source of an acid used for dissociation of the block, there is a disadvantage that the photoacid generator or the thermal acid generator is expensive and has poor solubility. Also, many of them are unsuitable for firing because they are compounds containing halogen.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art, and the main object of the present invention is to provide excellent photocurability and extremely large amounts of inorganic fine powder. Demonstrates excellent depth of cure and excellent storage stability even when it contains a body, and exhibits stable adhesion to the substrate in each of the drying, exposure, development, and baking steps, and developability and development resistance to alkali developing solutions sex,
An object of the present invention is to provide a composite pattern layer capable of obtaining a high-definition, high-aspect-ratio pattern excellent in sinterability and the like, and a method for producing the same.

[0007]

Means for Solving the Problems According to a first aspect of the present invention, (A) an alkali-developable photosensitive resin composition containing an acid, and (B) a photocurable composition which is decomposed by an acid and becomes alkali-soluble. And a photosensitive resin composition containing a conductive resin.
The acid of the composition of the acid (A) is preferably an acid stronger than carboxylic acid, more preferably inorganic phosphoric acid, and more specifically, hypophosphorous acid. A composite pattern layer is provided.

According to another embodiment, the photosensitive resin composition constituting the layer (B) of the photosensitive resin composition containing a photocurable resin which is decomposed by an acid and becomes alkali-soluble is (b)
1) a photocurable resin that is decomposed by an acid to become alkali-soluble, (b2) an inorganic powder, (b3) a photopolymerizable monomer,
A composite pattern layer comprising (b4) a photopolymerization initiator and (b5) an organic solvent is provided. Preferably,
The photosensitive resin composition constituting the layer (B) of the photosensitive resin composition containing the photocurable resin which is decomposed by an acid and becomes alkali-soluble is formed. The composite pattern layer is provided, wherein the conductive resin (b1) is a polycarboxylic acid resin in which a carboxyl group is blocked.

According to another aspect of the present invention, a layer (A) of an alkali-developable photosensitive resin composition containing an acid on a substrate,
A method of forming a composite layer comprising a layer (B) of a photosensitive resin composition containing a photocurable resin which is decomposed by an acid and becomes alkali-soluble, and exposing and developing the formed composite layer to form a pattern; 90 ° C to 150 ° C after exposure and before development
And a method for producing a composite pattern layer, characterized in that a heat treatment is performed.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, in a conventional alkali developing type composition, a portion cured by exposure also has a group having solubility in alkali, so that a pattern layer using such a composition is Undercut is likely to occur, and the difference in alkali solubility between the exposed and unexposed areas is not sufficient. Therefore, the setting of the developing time is narrow, and the resolution is limited. In this regard, in the present invention, the pattern forming layer contains an alkali-developable photosensitive resin composition (A) containing a halogen-free acid stronger than carboxylic acid, and a photocurable resin that is decomposed by an acid and becomes alkali-soluble. It is characterized in that it is a composite pattern layer having a two-layer structure formed from the photosensitive resin composition (B). Thereby, the setting of the developing time is wide, and a high-definition pattern can be formed.

The composite pattern layer having the two-layer structure is
From a layer composed of an alkali-developable photosensitive resin composition (A) containing a halogen-free acid stronger than carboxylic acid, a photosensitive resin composition (B) containing a photocurable resin that is decomposed by an acid and becomes alkali-soluble Hydrogen ions gradually diffuse into the layer consisting of and promote the dissociation of the block, but at room temperature,
The dissociation of the block is slow, and if heated after exposure, the dissociation of the block proceeds rapidly, and the carboxylic acid is developed, enabling alkali development. At this time, the curing of the exposed portion is progressing due to the crosslinking of the photocurable unsaturated double bond due to polymerization, so that the block is slowly dissociated even when heated. For this reason, the exposed portion is hardly dissolved in alkali, and peeling and surface erosion during development are unlikely to occur. On the other hand, since the unexposed portion has no curing due to the crosslinking of the unsaturated double bond, the dissociation of the block due to heating proceeds compared to the exposed portion, so that good developability is obtained, and thus high resolution is obtained. A high-definition pattern can be formed.

Hereinafter, the present invention will be described in detail. Alkali-developing photosensitive resin composition containing acid of the present invention (A)
Examples of the composition include a composition comprising at least (a1) a resin having alkali solubility and (a2) an acid. In these compositions, if necessary, (a3) a photopolymerizable monomer whose main purpose is to improve the reactivity and adjust the viscosity, (a4) a photopolymerization initiator whose purpose is to promote photopolymerization, and adjust the viscosity. (A5) An organic solvent whose main purpose is to improve coating workability, a glass frit as a firing pattern forming material, a metal fine powder such as a silver powder as an electrode forming material, and the like can be used.

The alkali-soluble resin (a1)
Examples thereof include copolymers of acrylic acid and methacrylic acid and other compounds having a polymerizable property, resins obtained by subjecting them to a compound having a glycidyl group and a compound having a polymerizable unsaturated double bond, and polymerizable unsaturated diacrylates. Polybasic acid having a heavy bond or a copolymer of an anhydride thereof and a resin obtained by reacting them with a compound having a hydroxyl group or an amino group and a polymerizable unsaturated double bond, a glycidyl group and an unsaturated double bond. A monobasic acid having a polymerizable unsaturated double bond is reacted with a copolymer of a compound having the compound and another compound having an unsaturated double bond, and further, a polybasic acid anhydride is added to a hydroxyl group generated by the reaction. And a novolak-type epoxy resin are reacted with a compound having a polymerizable unsaturated double bond and a carboxyl group such as acrylic acid. Such photocurable polycarboxylic acid resin produced by reacting an acid anhydride.

Examples of the acid (a2) include metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, phosphorous acid, hypophosphorous acid, orthophosphoric acid, diphosphoric acid, tripolyphosphoric acid,
Such as inorganic phosphoric acid, methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dipropyl phosphate, diphenyl phosphate, and isopropyl phosphate , Diisopropyl phosphate, n-butyl phosphate, methyl phosphite, ethyl phosphite, propyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, phosphorous acid Dibutyl, dipropyl phosphite, diphenyl phosphite, isopropyl phosphite, diisopropyl phosphite, n-butyl-2-ethylhexyl phosphite, hydroxyethylenediphosphonic acid, adenosine triphosphate, adenosine phosphate, Mono (methacryloyloxyethyl) acid phosphate, mono (acryloyloxyethyl) acid phosphate Fate, di (methacryloyloxyethyl) acid phosphate, di (acryloyloxyethyl) acid phosphate, ethyl diethyl phosphonoacetate, ethyl acid phosphate, butyl acid phosphate, butyl pyrophosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, oleyl Organic phosphates such as acid phosphate, tetracosyl acid phosphate, diethylene glycol acid phosphate, (2-hydroxyethyl) methacrylate acid phosphate, and the like can be mentioned. From the viewpoint of stability, inorganic phosphoric acid is preferable, and hypophosphorous acid is more preferable in consideration of the influence on various properties.

The photopolymerizable monomer (a3) includes:
For example, hydroxyl-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate; water-soluble acrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; Polyfunctional polyester acrylates of polyhydric alcohols such as methylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate; polyfunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol Of ethylene oxide adduct and / or propylene oxide adduct of Polyfunctional or monofunctional polyurethane acrylate which is an isocyanate modified product of the above-mentioned hydroxyl group-containing acrylate; epoxy which is a (meth) acrylic acid adduct of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolak epoxy resin Examples include acrylates and methacrylates corresponding to the above acrylates, and these can be used alone or in combination of two or more. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule is preferable.

Examples of the photopolymerization initiator (a4) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone. Acetophenones such as 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-
2-dimethylamino-1- (4-morpholinophenyl)
Aminoacetophenones such as -butan-1-one and N, N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Dimethylthioxanthone, 2,4
Thioxanthones such as diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; organic peroxides such as benzoyl peroxide and cumene peroxide;
Thiol compounds such as 4,5-triarylimidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; 2,4,6-
Organic halogen compounds such as tris-s-triazine, 2,2,2-tribromoethanol and tribromomethylphenylsulfone; benzophenones such as benzophenone and 4,4'-bisdiethylaminobenzophenone; and xanthones; 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide and the like. These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more thereof. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-ethyl ester Photoinitiating aids such as tertiary amines such as dimethylaminobenzoate, triethylamine and triethanolamine can be added. In addition, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) which absorbs in the visible light region can also be added to promote the photoreaction. A particularly preferred photopolymerization initiator is 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl) -butan-1-one and the like, but are not particularly limited thereto, and absorbs light in an ultraviolet light or visible light region to form an unsaturated group such as a (meth) acryloyl group. As long as they cause radical polymerization, they are not limited to a photopolymerization initiator and a photoinitiator, but can be used alone or in combination.

The organic solvent (a5) can be blended in order to adjust the composition to a viscosity suitable for a coating method. Examples of the organic solvent (a5) include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene;
Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol mono Glycol ethers such as ethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomer Acetic acid esters such as ether ether and dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, And petroleum solvents such as solvent naphtha.

As the photosensitive resin composition (B) containing a photocurable resin which is decomposed by an acid and becomes alkali-soluble, (b1) a photocurable resin which is decomposed by an acid and becomes alkali-soluble, (b2) Inorganic powder, (b3) a photopolymerizable monomer, (b4) a photopolymerization initiator, (b5) an acid multiplying agent, (b
6) A composition characterized by containing an organic solvent.

The photocurable resin (b1) which is decomposed by an acid and becomes alkali-soluble is a novolak type phenol resin or a polymer derived from vinyl phenol.
Examples thereof include polymers having an tert-butoxycarbonyl ester group, copolymers of (meth) acrylic acid and tert-butyl esters, and polymers obtained by adding a monovinyl ether compound to a copolymer of (meth) acrylic acid.
In a preferred embodiment, the solid content acid value is 60 to 300 mgK.
OH / g and a weight average molecular weight of about 1,000 to 5
A resin obtained by reacting a monovinyl ether compound with 0000 polycarboxylic acid resin is used. In this resin, the carboxyl group of the polycarboxylic acid resin is blocked by a monovinyl ether compound. After the film is formed, when it is decomposed by irradiation with active energy rays and heating, it expresses a free carboxyl group and is soluble in an alkaline aqueous solution. Return to the polycarboxylic acid resin.

As the polycarboxylic acid resin, preferably, a copolymer resin containing 8 to 40% by weight of acrylic acid and / or methacrylic acid and another monomer is used. Other monomers include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, tet-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, nonyl acrylate, dodecyl acrylate, octyl acrylate, isobornyl acrylate, -Hydroxyethyl acrylate, 2-hydroxymethyl acrylate, 3
Acrylates such as -chloro-2-hydroxypropyl acrylate or methacrylates corresponding thereto, styrenes such as styrene, chlorostyrene, α-methylstyrene, polyethylene glycol, polypropylene glycol, and the like, and monoacrylates of their ethylene oxide or propylene oxide adducts Or monovinyl compounds such as monomethacrylate, vinyl acetate, vinyl butyrate or vinyl benzoate; olefins such as ethylene and propylene; and polymerizable amine compounds such as acrylonitrile and melamine acrylate. These monomers can be used alone or in combination of two or more.

The monovinyl compound includes vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl-n-propyl ether,
Examples thereof include vinyl isobutyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, ethylene glycol butyl vinyl ether, and triethylene glycol monomethyl vinyl ether. Monovinyl ether having a boiling point of 30 to 200 ° C is preferable. When the boiling point of the monovinyl ether compound is lower than 30 ° C., it is difficult to add the monovinyl ether compound to the polycarboxylic acid resin when synthesizing the photocurable resin (b1) which is decomposed by the acid and becomes alkali-soluble. On the other hand, the boiling point is 200 ° C
When it exceeds, the monovinyl ether compound generated by the thermal decomposition of the photocurable resin (b1) which is decomposed by the acid and becomes alkali-soluble during the heat treatment of the coating film is converted into the polycarboxylic acid resin similarly generated. A reversible reaction of re-addition occurs, which makes it difficult to develop the exposed portion of the coating film with a weak alkaline aqueous solution, which is not preferable.

As the inorganic powder (b2), for example,
Glass powder containing lead oxide, bismuth oxide, or zinc oxide as a main component, alumina, cordierite, ceramic powder such as zircon, Cu, Fe, Cr, Mn, Co, Ni,
Oxides such as Ru, composite oxides, lanthanum bolite (L
black pigments such as aB ₆ ) and silver (Ag), gold (Au),
Nickel (Ni), copper (Cu), aluminum (A
l), tin (Sn), lead (Pb), zinc (Zn), iron (F
e), simple substances and alloys such as platinum (Pt), iridium (Ir), osmium (Os), palladium (Pd), rhodium (Rh), ruthenium (Ru), tungsten (W), molybdenum (Mo), Tin oxide (SnO ₂ ),
Indium oxide (In ₂ O ₃ ), ITO (Indium Tin O
xide) or the like.

The glass powder containing lead oxide as a main component is preferred.
A good example is PbO of 4% by weight on an oxide basis.
8 to 82%, B_TwoO_ThreeIs 0.5 to 22%, SiO_TwoIs 3 ~
32%, Al_TwoO_ThreeIs 0 to 12%, BaO is 0 to 10%,
0-15% ZnO, TiO _TwoIs 0 to 2.5%, Bi_TwoO
_ThreeHas a composition of 0 to 25% and a softening point of 420 to 590.
Non-crystalline frit that is at ° C.

Preferred examples of the glass powder containing bismuth oxide as a main component include Bi in terms of weight% on an oxide basis.
₂ O ₃ is thirty-five to eighty-eight% B ₂ O ₃ is 5 to 30% SiO ₂ is 0 to 20% Al ₂ O ₃ 0 to 5 percent, BaO 1 to 25
%, ZnO having a composition of 1 to 20%, and a softening point of 520.
Amorphous frit having a temperature of ５590 ° C.

Preferable examples of the glass powder containing zinc oxide as a main component include ZnO of 25 to 60%, K ₂ O of 2 to 15%, and B ₂ O ₃ of 25 to 4
5%, SiO ₂ is 1~7%, Al ₂ O ₃ is 0%, B
aO has a composition of 0 to 20%, MgO has a composition of 0 to 10%,
An amorphous frit having a softening point of 420 to 590 ° C is exemplified. Note that, in addition to the above glass components, glass containing lithium, fluorine, phosphorus, sodium, and potassium can also be used.

It is desirable to use the ceramic powder having an average particle diameter of 10 μm or less, preferably 2.5 μm or less from the viewpoint of resolution. Also, this ceramic powder
It is preferable to use the glass powder in an amount of 1 to 100 parts by weight based on 100 parts by weight of the glass powder. Similarly, it is desirable to use a black pigment having an average particle diameter of 20 μm or less, preferably 5 μm or less from the viewpoint of resolution. When this black pigment is used, it is preferable to use the black pigment in a mixing ratio of 1 to 100 parts by weight with respect to 100 parts by weight of the glass powder.

As the shape of the conductive powder, various shapes such as a spherical shape, a flake shape and a dendrite shape can be used, but it is preferable to use a spherical shape in consideration of optical characteristics and dispersibility. Further, it is desirable to use an average particle diameter of 20 μm or less, preferably 5 μm or less from the viewpoint of resolution. In addition, in order to prevent oxidation of the conductive metal powder, improve dispersibility in the composition, and stabilize the developing property, Ag,
Ni and Al are preferably treated with fatty acids. Fatty acids include oleic acid, linoleic acid, linoleic acid, stearic acid and the like. The amount of the conductive powder is 5 to 100 parts by weight of the photocurable resin (b1) which is decomposed by the acid and becomes alkali-soluble.
A ratio of not more than 00 parts by weight is appropriate. If the amount is more than 500 parts by weight, light transmittance is impaired, and it becomes difficult to obtain photocurability of the composition, which is not preferable.

As the photopolymerizable monomer (b3),
The same as those listed as the photopolymerizable monomer (a3) can be used.

As the photopolymerization initiator (b4), those similar to those listed as the photopolymerization initiator (a4) can be used.

As the organic solvent (b5), those similar to those listed as the organic solvent (a5) can be used.

The photosensitive resin composition (B) containing the photocurable resin which is decomposed by an acid and becomes alkali-soluble according to the present invention.
May be mixed with an acid proliferating agent for the purpose of accelerating the decomposition. Examples of the acid proliferating agent include JP-A-8-248561.
JP, JP-A-11-158118, JP-A-200
Acetoacetate derivatives, ketal sulfonate derivatives,
Examples thereof include a 2-diol monosulfonate derivative and a crosslinked carbocyclic compound having a sulfonate group.

In addition, the alkali-developable photosensitive resin composition (A) of the present invention and the photosensitive resin composition (B) containing a photocurable resin which is decomposed by an acid to become alkali-soluble are added to the desired composition. In addition to additives such as silicone-based and acrylic-based antifoaming agents and leveling agents, and silane coupling agents for the purpose of improving the adhesion of the film, as well as light scattering prevention, as long as the properties are not impaired. For this purpose, organic dyes and organic pigments, and fine particles of silicon oxide, boron oxide, or the like as a binding component with the substrate during firing can be blended.

Hereinafter, the production method of the present invention will be specifically described. First, each of the compositions (A) and (B) composed of the above-mentioned compositions is blended and adjusted by an appropriate method such as a ball mill, a three-roll mill, a butterfly mixer, a sand mill, and a grinder. Then, the prepared composition (A) is applied to an appropriate substrate such as a glass substrate or a ceramic substrate by an appropriate method such as a roll coating method, a bar coating method, a screen printing method, a curtain coating method, a spray coating method, or a dip coating method. Apply and apply in a suitable method, for example, 60-1
It is dried for 10 to 30 minutes in a hot air circulation type drying furnace at 00 ° C. Once cooled to the working temperature, the prepared composition (B) is applied and dried using the same method as the composition (A), and then cooled to the working temperature. A negative film for pattern formation is brought into close contact with the dried coating film of the composition (B), irradiated with active energy rays such as ultraviolet rays, selectively cured by light, the negative film is peeled off, and then a hot-air circulating drying oven, etc. By using an appropriate method, heating is performed at 90 to 150 ° C. for 5 to 60 minutes to accelerate the dissociation of the block, and thereafter, development is performed with an aqueous alkali solution.

As the alkaline aqueous solution, an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used. Further, as an irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, a laser beam or the like can be used as the active energy ray.

When the composite pattern layer of the present invention is used for a plasma display panel application, after development, the substrate is subjected to a heat treatment at 450 to 600 ° C. in air or a nitrogen atmosphere to remove organic substances and sinter. Form a body pattern.

[0036]

The present invention will be described more specifically with reference to Composition Examples 1 and 2 and Comparative Composition Example 1. Unless noted otherwise,
“Parts” represents “parts by weight”. Synthesis Example 1 Diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst were placed in a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, and heated to 80 ° C. under a nitrogen atmosphere. , A monomer obtained by mixing 69 parts (0.8 mol) of methacrylic acid and 120 parts (1.2 mol) of methyl methacrylate was added to about 2 parts.
The mixture was added dropwise over a period of time, and after further stirring for 1 hour, the temperature was increased to 115
C. and deactivated to obtain a resin solution. After cooling the resin solution, 104 parts of butyl glycidyl ether (0.8 parts
Mol) was reacted with a carboxyl group of the obtained resin at 95 to 105 ° C. for 30 hours. Further, 80 parts (0.52 mol) of tetrahydrophthalic anhydride was added to the OH group of the resin obtained by the reaction at 95 to 105 ° C. for 8 hours to give a weight average molecular weight of 35,000 and an acid value of the solid of 78. 1
A resin solution having a mgKOH / g concentration of 50% solids was obtained.
This resin solution is referred to as varnish A.

Synthesis Example 2 362.7 parts of dipropylene glycol monomethyl ether and 11.5 parts of azobisisobutyronitrile were placed in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser.
And heated to 75 ° C. There, acrylic acid 7
A mixed solution of 2.0 parts and 215.7 parts of methyl methacrylate was obtained. The obtained copolymer resin has a weight average molecular weight of 1
At 6,000, the acid value was 193 mg KOH / g.
After cooling the resin solution to room temperature, 150 parts of vinyl isobutyl ether was added and reacted at 50 ° C. for 30 hours to confirm by acid value measurement that vinyl isobutyl ether was added to 75% of the carboxyl groups of the resin. did. Unreacted vinyl isobutyl ether remaining in the reaction solution was removed under reduced pressure by an evaporator to obtain a resin solution. This resin solution is referred to as varnish B.

Composition Example 1 (Acid-containing photosensitive composition containing an acid) Acrylic copolymer resin Varnish A 100 parts Trimethylolpropane triacrylate 30 parts 2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -butan-1-one 10 parts Black pigment (Cu-Cr-Co composite oxide) 100 parts Hypophosphorous acid 5 parts Diethylene glycol monoethyl ether acetate 60 parts

Composition Example 2 (Photosensitive resin composition containing a photocurable resin which is decomposed by an acid and becomes alkali-soluble) Block carboxylic acid resin Varnish B 100 parts Trimethylolpropane triacrylate 30 parts 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one 10 parts Silver powder (silver powder having an average particle diameter of 1 μm treated with a fatty acid) 100 parts Glass frit (average particle diameter 2 μm, Bi) ₂ O ₃ —B ₂ O ₃ —SiO ₂ —ZnO—BaO system) 25 parts Diethylene glycol monoethyl ether acetate 70 parts

Comparative Composition Example 1 Acrylic Copolymer Resin Varnish A 100 parts Trimethylolpropane triacrylate 30 parts 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one 10 parts Silver Powder (silver powder having an average particle diameter of 1 μm treated with a fatty acid) 100 parts Glass frit (average particle diameter 2 μm, Bi ₂ O ₃ —B ₂ O ₃ —SiO ₂ —ZnO—BaO system) 25 parts Diethylene glycol monoethyl ether 70 parts of acetate

The components were blended in the composition ratios described in Composition Examples 1 and 2 and Comparative Composition Example 1, and stirred with a stirrer.
This roll mill was used to make meat and paste. Using each of the pastes thus obtained, an evaluation substrate was prepared under the following conditions, and the resolution and the line shape after firing were evaluated. The preparation conditions and evaluation results are as follows. Preparation conditions: The paste composition of the above composition example 1 was applied on the entire surface of a glass substrate using a 300-mesh polyester screen, and the formed coating film was heated for 15 minutes using a hot-air circulation drying oven at 80 ° C. Dry to form the first layer. Once cooled to room temperature to obtain a good dryness to the touch, then apply the paste composition of Composition Example 2 or Comparative Composition Example 1 to the entire surface using a screen in the same manner as in the formation of the first layer. Then, the formed coating film was dried using a hot-air circulating drying oven at 80 ° C. for 20 minutes to form a second layer, thereby obtaining a composite pattern layer having good dryness to the touch. Next, the line / space is from 10/10 (μm / μm) to 100/100 (μm / μm /
μm), exposure was performed so that the integrated exposure amount became 700 mJ / cm ² (manufactured by Oak Manufacturing Co., Ltd., model HMW-680GW), and the examples (compositions were used) using a hot-air circulation drying oven. For the composite pattern layer composed of Example 1 and Composition Example 2), the dissociation accelerating temperature condition 1
In a combination of 10 ° C. and 140 ° C., a heating time of 5 minutes and 30 minutes, and a developing time of 60 seconds and 90 seconds, for the comparative example (composite pattern layer composed of the composition example 1 and the comparative composition example 1), Since no heating was performed, the test was conducted with a development time of 60 seconds and 90 seconds. The development was performed with 1 wt% Na at a liquid temperature of 30 ° C.
Using an aqueous ₂ CO ₃ solution at a spray pressure of 2.0 Kg / cm ² , washing was performed with water. Then, at 450 ° C. in air for 30 minutes.
After heating for one minute, the resultant was baked by heating at 550 ° C. for 30 minutes.

Evaluation method: Resolution Evaluation was made based on the remaining lines and missing spaces with respect to the lines / spaces of the film after development, and the line / space size (μm) having no problem was used as the evaluation result of the resolution.

Line shape after firing The film after firing was evaluated for warpage and peeling (or cracking) according to the following criteria. ：: warpage in the cross-sectional shape of the stripe pattern and no peeling off △: slight warpage in the cross-sectional shape of the stripe pattern 10
%: Exfoliation of less than%: The cross-sectional shape of the stripe pattern is warped. Or, peeling or cracking of 10% or more has occurred remarkably.

Table 1 shows the obtained results.

[Table 1]

In the above embodiment, the conductive glass paste was described. However, it is needless to say that the present invention is not limited to this, and the present invention is also useful as a glass paste for PDP, a paste for forming a black pattern, and the like. In addition, the present invention can be applied to formation of an insulating layer of a multilayer printed wiring board, manufacture of a liquid crystal panel, and the like.

[0046]

According to the present invention as described above,
The two-layered film formed by combining an alkali-developable photosensitive resin composition containing an acid and a photocurable resin composition that is decomposed by an acid and becomes alkali-soluble is particularly different because it is excellent in forming a high-definition pattern. A high-definition conductive pattern can be stably formed with high yield on a large-area substrate formed of two layers.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 511 G03F 7/004 511 H01J 9/02 H01J 9/02 F 11/02 11/02 B 17 / 04 17/04 F-term (reference) 2H025 AA01 AA02 AA03 AA04 AA14 AB20 AC01 AD01 BC13 BC42 BJ01 CA00 CB14 CB41 CB51 CC03 CC08 CC20 FA12 FA17 FA29 4J011 AC04 PA02 PA69 PA85 PB06 PB22 PC02 QA24 QA23 QA24 QA24 QA24 QA24 SA02 SA03 SA04 SA06 SA12 SA13 SA15 SA17 SA19 SA32 SA34 SA54 SA58 SA63 SA64 SA76 SA78 SA83 SA84 UA01 VA01 WA01 4J026 AA43 AA45 AB01 AC09 AC23 AC36 BA27 BA28 BA30 BA50 DB02 DB06 DB09 DB11 DB30 DB36 FA05 GA09 5C027 AA01 GB02 GB05 JA05 JA12 JA15 MA02 MA22 MA23 MA24

Claims (7)

[Claims] 1. A photosensitive resin composition comprising (A) an alkali-developable photosensitive resin composition containing an acid, and (B) a photosensitive resin composition containing a photocurable resin which is decomposed by an acid and becomes alkali-soluble. A composite pattern layer, comprising: 2. The composite pattern layer according to claim 1, wherein the acid is a stronger acid than a carboxylic acid. 3. The composite pattern layer according to claim 2, wherein the acid stronger than the carboxylic acid is inorganic phosphoric acid. 4. The composite pattern layer according to claim 2, wherein hypophosphorous acid is contained as an acid stronger than carboxylic acid. 5. The photosensitive resin composition constituting the layer (B) comprises:
(B1) a photocurable resin which is decomposed by an acid to become alkali-soluble, (b2) an inorganic powder, (b3) a photopolymerizable monomer, (b4) a photopolymerization initiator, and (b5) an organic solvent. The composite pattern layer according to claim 1. 6. The composite pattern layer according to claim 5, wherein the photocurable resin (b1) which is decomposed by an acid and becomes alkali-soluble is a polycarboxylic acid resin having a carboxyl group blocked. 7. A photosensitive resin composition comprising (A) an alkali-developable photosensitive resin composition containing an acid and (B) a photocurable resin which is decomposed by an acid to become alkali-soluble. Forming a composite layer comprising: exposing and developing the composite layer to form a pattern, wherein the pattern is subjected to a heat treatment at 90 ° C. to 150 ° C. after exposure and before development. The method of manufacturing the layer.