JP2005332696A - Forming method of display member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a forming method of a barrier rib of a back plate of a plasma display in which exposure time is shortened by reducing light exposure amount at the time of formation of the barrier rib pattern, thereby shortening the time required for formation of the barrier rib pattern. <P>SOLUTION: The formation method of a barrier rib comprises a process of coating and drying a light sensitive paste containing inorganic particles on a substrate, a process of exposing using a mask, a process of developing an unexposed part, and a process of calcining the pattern obtained after development. In the process of exposure using a mask, the substrate is heated to a range of 40°C-150°C to form the display member. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for forming a display member.

In recent years, miniaturization and high definition have progressed in displays, and accordingly, improvement of pattern processing technology is desired. As a pattern processing technique, for example, a photosensitive paste method is known, which is used for forming a partition wall of a back plate which is a plasma display member.
As a method of forming the partition wall of the back plate of the plasma display, for example, a photosensitive paste containing acrylic acid-styrene copolymer polymer, glass powder, and a photopolymerization initiator is applied on a substrate, exposed and developed. A method of forming a partition wall pattern and firing it to form a partition wall is known (see Patent Document 1).
However, conventionally used exposure machines are derived from semiconductor manufacturing, and if heated during exposure, the mask for pattern formation is distorted due to heat and the pattern transfer accuracy does not come out, or the substrate and From the viewpoint that thermal convection occurs in the gap with the mask and resolution does not come out, an exposure machine equipped with a heating device has not been used.

JP, 2001-22064, page 9, right column, line 27, page 10-left column, line 11

However, in the method described in Patent Document 1, the present inventor has found that the exposure time is long because the exposure amount at the time of forming the partition wall pattern is large.
It is an object of the present invention to shorten the exposure time by reducing the amount of exposure at the time of forming a partition wall pattern, thereby reducing the time required for forming the partition wall pattern, and a plasma display member such as a method for forming partition walls on a back plate of a plasma display. It is in providing the formation method.

  The present inventor has intensively studied to find a method for shortening the exposure time at the time of forming the partition wall pattern, and as a result, has found that the exposure amount can be reduced by heating the substrate at the time of exposure, thereby completing the present invention. It came.

  That is, the present invention includes a step of applying and drying a photosensitive paste containing inorganic particles on a substrate, a step of exposing using a mask, a step of developing an unexposed portion, and a pattern obtained after development. In the method for forming the partition comprising the step of baking, the exposure apparatus provided with the display member forming method for heating the substrate to 40 ° C. to 150 ° C. in the step of exposing using a mask and the heating device used in the forming method I will provide a.

  According to the present invention, it is possible to reduce the exposure amount at the time of forming a partition wall pattern, which is a display member using a photosensitive paste, thereby shortening the exposure time.

Hereinafter, the present invention will be described in detail.
First, a photosensitive paste is applied on the entire surface or a part of the substrate. As the substrate, soda glass, borosilicate glass, Pyrex glass (registered trademark), high strain point glass for PDP, non-alkali glass, or the like can be used.
Furthermore, a dielectric layer may be formed on the substrate.

  As a coating method, for example, a method using a device such as a bar coater, a roll coater, a die coater, or screen printing can be applied. The thickness of the film to be applied can be appropriately adjusted by selecting the number of times of application and the viscosity of the paste, and is usually 5 to 500 μm.

When applying the photosensitive paste onto the substrate, it is preferable to treat the surface of the substrate with a surface treatment liquid in order to improve the adhesion between the substrate and the coating film of the photosensitive paste.
Examples of the surface treatment liquid include silane coupling agents such as glycidyloxypropyltriethoxysilane, glycidyloxypropyltrimethoxysilane, and oxetanyloxypropyltriethoxysilane. As the silane coupling agent, it is preferable to use a silane coupling agent diluted to a concentration of 0.1 to 5% by mass with an organic solvent such as ethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol.
Examples of the surface treatment method include a method in which a surface treatment liquid is uniformly applied on a substrate with a spinner or the like and then dried at 80 to 140 ° C. for 5 to 60 minutes.
The photosensitive paste applied on the substrate can be dried at a temperature of 60 to 150 ° C. for 10 to 120 minutes using a hot plate, a circulation oven, an IR oven or the like.

  After applying and drying the photosensitive paste, exposure is performed using an exposure apparatus while heating the substrate. The exposure apparatus is provided with a heating device for heating the substrate. Any heating device can be used without particular limitation as long as it can be exposed while heating the substrate, such as a hot plate or a silicon rubber heater. The heating temperature is usually 40 to 150 ° C, preferably 50 to 140 ° C, more preferably 60 to 130 ° C, and particularly preferably 60 to 100 ° C. It is preferable for the heating temperature to be in the above-mentioned range since the exposure amount can be reduced.

  Examples of the exposure apparatus include a proximity exposure machine. When exposing a large area, a large area can be exposed with an exposure machine having a small exposure area by applying a photosensitive paste on a substrate and then performing exposure while moving the photosensitive paste. As a light source used for exposure, for example, ultraviolet rays, electron beams, X-rays, visible light, near infrared light, and the like can be used.

After the exposure, development is performed using the difference in solubility between the exposed portion and the unexposed portion in the developer. Development is usually performed using an apparatus such as a dipping method, a spray method, or a brush method.
Examples of the developer include aqueous alkali solutions such as tetramethylammonium hydroxide, monoethanolamine, diethanolamine, sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate.
The alkali concentration in the aqueous solution is preferably 0.05 to 5% by mass, more preferably 0.1 to 5% by mass. When the alkali concentration is in the above range, the portion to be removed by development tends to be easily removed, and the portion to be left tends not to be peeled off or eroded, which is preferable.
The development temperature during development is preferably 15 to 50 ° C., more preferably 20 to 40 ° C. in terms of process control.

After the pattern is formed as described above, the partition walls can be formed by firing in a firing furnace. The firing atmosphere and firing temperature can be appropriately selected depending on the type of photosensitive paste and substrate, and firing is preferably performed at 400 to 600 ° C. in an atmosphere such as air or nitrogen. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.
In particular, when patterning on a glass substrate, firing is preferably performed at a temperature of 400 to 600 ° C. for 10 to 60 minutes.

  A coat layer may be formed on the surface of the obtained partition wall. The coating layer is formed by applying and drying a coating agent such as a paste agent or a ceramic coating agent composed of low-melting glass particles and a binder resin, and baking it to form on the surface of the partition wall, or after forming the above pattern, the coating agent It may be formed on the surface of the partition simultaneously with the formation of the partition by baking after applying.

As the ceramic coating agent, an aqueous metal salt-based coating agent, an alkoxy metal salt-based coating agent, or the like can be used. Specifically, as an aqueous metal salt-based coating agent, MS-1700, as an alkoxy metal salt-based coating agent. May include G-301 and G-401 (both manufactured by Nisera Corporation).
The firing temperature of the coating agent is usually 250 to 600 ° C. when a paste agent composed of low melting glass particles and a binder resin is used, and usually 20 to 500 ° C. when a ceramic coating agent is used. .

  The photosensitive paste used in the present invention preferably contains an alkali-soluble polyorganosiloxane resin composition and inorganic particles.

The alkali-soluble polyorganosiloxane resin composition is preferably a resin composition containing (A) and (B).
(A) a polyorganosiloxane resin having at least one functional group selected from the group consisting of a functional group represented by formula (1) and a functional group represented by formula (2) (B) a polyorgano having a hydroxyl group Siloxane resin

[In Formula (1) and Formula (2), A ¹ and A ² each independently represents an oxygen atom or a sulfur atom.
^{R a, R b, R '} a and ^{R' b} independently represent a divalent organic group.
R ^{1 to} R ⁸ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
l ₁ , m ₁ , l ₂ , and m ₂ each independently represents an integer of 0 or more and 20 or less. ]

Among the ^{R a, R b, R '} a and ^{R' b,} as the divalent organic group, a linear, branched, or cyclic, for example, methylene group, ethylene group, propylene Group, butylene group, pentylene group, hexylene group, isopropylene group, isobutylene group and other alkylene groups, cyclobutylene group, cyclopentylene group, cyclohexylene group and other cycloalkylene groups, phenylene group, naphthylene group, biphenylene group, alkyl And arylene groups such as substituted phenylene groups.

Among R ^{1 to} R ⁸ , the monovalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, for example, a linear aliphatic hydrocarbon having 1 to 20 carbon atoms. Group, a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like.
Moreover, the C6-C20 aromatic hydrocarbon group may be substituted with an alkyl group, an alkenyl group, or the like.
Among these, a straight hydrocarbon group having 1 to 6 carbon atoms, a branched hydrocarbon group having 3 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic carbon atom having 6 to 20 carbon atoms. A hydrogen group is preferred.

Examples of the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
Examples of the branched aliphatic hydrocarbon group having 3 to 20 carbon atoms include isopropyl group, isobutyl group, and tertiary butyl group.
Examples of the cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the substituent of the aromatic hydrocarbon group having 6 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, and alkenyl groups such as ethynyl group.
Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, a tolyl group, a xylyl group, a trimethylphenyl group, an ethylphenyl group, a diethylphenyl group, a triethylphenyl group, and a propylphenyl group. Butylphenyl group, methylnaphthyl group, dimethylnaphthyl group, trimethylnaphthyl group, vinylnaphthyl group, methylanthryl group, ethylanthryl group, and the like.

  Examples of the functional group represented by the formula (1) or (2) include oxiranyl group, glycidyl group, oxiranylethyl group, glycidyloxyethyl group, glycidyloxypropyl group, glycidyloxyphenyl group, oxetanyl group, (3′-methyl-3′-oxetanyl) methyl group, 2- (3′methyl-3′-oxetanyl) ethyl group, (3′methyl-3′-oxetanyl) methyloxyethyl group, (3′-methyl- 3′-oxetanyl) methyloxypropyl group, (3′-ethyl-3′-oxetanyl) methyl group, 2- (3′-ethyl-3′-oxetanyl) ethyl group, (3′-ethyl-3′-oxetanyl) ) Methyloxyethyl group, (3′-ethyl-3′-oxetanyl) methyloxypropyl group, and the like.

  (A) As the polyorganosiloxane resin containing at least one functional group selected from the group consisting of the functional group represented by the formula (1) and the functional group represented by (2), for example, poly [glycidyloxy Propylsilsesquioxane], poly [(3′-ethyl-3′-oxetanyl) methyloxypropylsilsesquioxane] and the like.

  (B) As polyorganosiloxane resin which has a hydroxyl group, resin which has the phenolic hydroxyl group represented by Formula (3) is mentioned, for example.

Wherein (3), A ³ represents an oxygen atom or a sulfur atom.
R ^{″ a} and R ^{″ b} each independently represents a divalent organic group.
R ^{9 to} R ¹² each independently represent a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 20 carbon atoms.
l ₃ and m ₃ each independently represents an integer of 0 or more and 20 or less. ]

In the formula (3), examples of the monovalent organic group having 1 to 20 carbon atoms include the same groups as described above.
Examples of the functional group represented by the formula (3) include a hydroxyphenyl group, a (hydroxyphenyl) methyl group, a 2- (hydroxyphenyl) ethyl group, a 1- (hydroxyphenyl) ethyl group, and 3- (hydroxyphenyl). A propyl group, 2- (hydroxyphenyl) propyl group, 1- (hydroxyphenyl) propyl group and the like can be mentioned.
Examples of the polyorganosiloxane resin having a functional group represented by the formula (3) include polysilsesquioxane having a dimethyl [2- (4′-hydroxyphenyl) ethyl] silyl group.

  Moreover, as (B) polyorganosiloxane resin which has a hydroxyl group, resin which has a hydroxyl group represented by following formula (4) is mentioned, for example.

[In Formula (4), R < ¹³ > -R < ¹⁸ > represents a hydrogen atom or a C1-C20 monovalent organic group each independently.
p and q each independently represents an integer of 0 or more and 20 or less.
r represents an integer of 1 or more and 20 or less. ]

Examples of the monovalent organic group having 1 to 20 carbon atoms include the same groups as described above.
p and q each independently preferably represent an integer of 0 to 15, more preferably an integer of 0 to 10.
r preferably represents an integer of 1 to 15, more preferably an integer of 1 to 10.

  Examples of the functional group represented by the formula (4) include a hydroxymethyl group, a hydroxyethyl group, a hydroxyethyloxyethyl group, and the like.

  Examples of the polyorganosiloxane resin having a functional group represented by the formula (4) include polysilsesquioxane having a dimethylhydroxyethyloxyethylsilyl group.

  As long as the resins (A) and (B) have the above-described functional groups, the main chain structure of the siloxane resin is not particularly limited, and linear, ladder-like, or cage-like resins may be used. it can.

  The structure represented by the formula (5) as the linear main chain structure, the structure represented by the formula (6) as the ladder-like main chain structure, and the structure represented by the formula (7) as the saddle-shaped main chain structure ) And the structure represented by each.

Wherein (5) to Formula ^(7), R 19 ^{to R 24} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ]

  The blending ratio of the polyorganosiloxane resin (A) and (B) in the alkali-soluble polyorganosiloxane resin composition is preferably (A) 5 to 85% by mass, (B) 15 to 95% by mass, and more. Preferably, they are (A) 10-70 mass% and (B) 30-90 mass%. A blending ratio in the above range is preferable because a pattern can be formed even with a thick film exceeding 50 μm.

  (A) The weight average molecular weight of the polyorganosiloxane resin containing at least one functional group selected from the group consisting of the functional group represented by formula (1) and the functional group represented by formula (2) is preferably It is 350-30,000, More preferably, it is 350-10,000.

(A) A polyorganosiloxane resin containing at least one functional group selected from the group consisting of a functional group represented by formula (1) and a functional group represented by formula (2) is represented by formula (1). And an alkoxysilane having at least one functional group selected from the group consisting of the functional group represented by the formula (2) is condensed in the presence of water using an acid catalyst or an alkali catalyst. Can be obtained. In the condensation, tetraalkoxysilane, trialkoxyorganosilane, dialkoxydiorganosilane, alkoxytriorganosilane, and the like may be co-condensed together.
Examples of the alkoxysilane having the functional group represented by the formula (1) or the functional group represented by the formula (2) include glycidyloxypropyltriethoxysilane and oxetanyloxypropyltriethoxysilane.

  Examples of the acid catalyst include hydrochloric acid and acetic acid. Examples of the alkali catalyst include ammonia and triethylamine.

Examples of tetraalkoxysilane include tetramethoxysilane and tetraethoxysilane.
Examples of trialkoxyorganosilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.
Examples of dialkoxydiorganosilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, ethylmethyldimethoxysilane, and ethylmethyldiethoxysilane.
Examples of the alkoxytriorganosilane include methoxytrimethylsilane, ethoxytrimethylsilane, methoxytriethylsilane, ethoxytriethylsilane, and ethyldimethylmethoxysilane.

In addition, the polyorganosiloxane resin having a functional group represented by the formula (1) is condensed with an organoalkoxysilane or organochlorosilane having an unsaturated bond in the molecule in the same manner as described above. It can also be obtained by oxidation. In the condensation, the above-mentioned tetraalkoxysilane, trialkoxyorganosilane, dialkoxydiorganosilane, alkoxytriorganosilane, etc. may be co-condensed.
Examples of the organoalkoxysilane or organochlorosilane having an unsaturated bond in the molecule include dimethylvinylethoxysilane, dimethylvinylchlorosilane, allyldimethylethoxysilane, and allyldimethylchlorosilane.
Examples of the peroxide include m-chloroperbenzoic acid.

(B) A polyorganosiloxane resin having a hydroxyl group is formed by condensing an organoalkoxysilane by the above method, and then reacting and sealing a terminal silanol group with a chlorosilane compound having a protected hydroxyl group. Can be obtained by deprotection.
It can also be obtained by condensing an organoalkoxysilane having a protected hydroxyl group in the same manner as described above and then deprotecting the hydroxyl-protecting group.

  Here, examples of the organoalkoxysilane include organomethoxysilane and organoethoxysilane. Specific examples include tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, and dimethyldimethoxy. Silane, trimethylethoxysilane, trimethylmethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, triethylethoxysilane, triethylmethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldiethoxy Silane, diphenyldimethoxysilane, triphenylethoxysilane, triphenylmethoxysilane, methylphenyldiethoxysilane Methylphenyl dimethoxysilane, dimethyl phenyl silane, dimethyl phenyl silane and the like.

A chlorosilane compound having a protected hydroxyl group is obtained by hydrosilylating a compound having a protected hydroxyl group and an unsaturated bond such as a vinyl group or an allyl group with a dialkylchlorohydrosilane compound in the presence of a transition metal catalyst. Can be manufactured.
A chlorosilane compound having a protected hydroxyl group can also be produced by a condensation reaction between an organometallic compound having a hydroxyl group protected in the molecule and a dialkyldichlorosilane compound.

Examples of the hydroxyl protecting group include an alkyl group, a silyl group, an acyl group, and an alkyloxycarbonyl group.
Specific examples of the hydroxyl-protecting group include a methoxymethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, 2,2,2-trichloroethoxymethyl group, 2- (trimethylsilyl). ) Ethoxymethyl group, tetrahydropyranyl group, 3-bromotetrahydropyranyl group, tetrahydrothiopyranyl group, 4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, 1-ethoxyethyl group, 1- Methyl-1-methoxyethyl group, 1- (isopropoxy) ethyl group, 2,2,2-trichloroethyl group, 2- (phenylselenyl) ethyl group, t-butyl group, benzyl group, 3-methyl-2 -Picolyl N-oxide group, diphenylmethyl group, 5-dibenzosuberyl group, triphenylmethyl group, 9-anne Ryl, trimethylsilyl, triethylsilyl, isopropyldimethylsilyl, t-butyldimethylsilyl, (triphenylmethyl) dimethylsilyl, t-butyldiphenylsilyl, methyldiisopropylsilyl, methyldit-butylsilyl, tri Benzylsilyl group, triisopropylsilyl group, triphenylsilyl group, formyl group, acetyl group, 3-phenylpropionate group, 3-benzoylpropionate group, isobutyrate group, 4-oxopentanoate group, pivaloate group, adamant Examples include an ate group, a benzoate group, a methoxycarbonyl group, an ethoxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, and an isobutyloxycarbonyl group.
Examples of the chlorosilane compound in which the active hydrogen atom of the functional group represented by the formula (3) is protected include 2- (4′-trimethylsilyloxyphenyl) ethyldimethylchlorosilane, [2- (4′-t-butoxyphenyl). ) Ethyl] dimethylchlorosilane and the like.

  In addition to (A) and (B), the alkali-soluble polyorganosiloxane resin composition further comprises (D) a functional group represented by the formula (1) and a functional group represented by the formula (2). And at least one functional group selected from the group consisting of a functional group represented by formula (3) and a functional group represented by formula (8). An alkali-soluble polyorganosiloxane resin may be contained.

Wherein (8), A ₄ represents an oxygen atom or a sulfur atom.
R ′ ″ _a and R ′ ″ _b each independently represent a divalent organic group.
l ₄ and m ₄ each independently represents an integer of 0 or more and 20 or less. ]

R ′ ″ _a and R ′ ″ _b each independently represent a divalent organic group, and examples of the divalent organic group include the same groups as described above.
l ₄ and m ₄ each independently preferably represent an integer of 0 to 15, preferably an integer of 0 to 10.

  (D) The polystyrene-converted weight average molecular weight of the alkali-soluble polyorganosiloxane resin is preferably 1,000 to 50,000, more preferably 1,000 to 30,000.

  (D) The alkali-soluble polyorganosiloxane resin is at least one functional group selected from the group consisting of the functional group represented by the formula (1) and the functional group represented by the formula (2) produced by the method described above. The active hydrogen of at least one functional group selected from the group consisting of the functional group represented by formula (3) and the functional group represented by formula (8) is used as the terminal silanol group of the polyorganosiloxane resin containing It can be obtained by reacting with an atom-protected chlorosilane compound, sealing, and deprotecting the protecting group.

  Further, (D) the alkali-soluble polyorganosiloxane resin comprises an alkoxysilane having a functional group represented by formula (1) or formula (2) and a functional group represented by formula (3) or formula (8). It can also be obtained by condensing the alkoxysilane having the above-mentioned method.

Examples of the chlorosilane compound in which the active hydrogen atom of the functional group represented by the formula (3) is protected include 2- (4′-trimethylsilyloxyphenyl) ethyldimethylchlorosilane, [2- (4′-t-butoxyphenyl). ) Ethyl] dimethylchlorosilane and the like.
Examples of the chlorosilane compound in which the active hydrogen atom of the functional group represented by the formula (8) is protected include trimethylsilyloxycarbonylpropyldimethylchlorosilane.
Examples of the (D) alkali-soluble polyorganosiloxane resin include polysilsesquioxane having (3′-ethyl-3′-oxetanyl) methyloxypropyl group and carboxypropyl group.

The alkali-soluble polyorganosiloxane resin composition has the above-mentioned (B) polyorganosiloxane resin having a hydroxyl group and (C) two or more functional groups represented by the formula (1) in the molecule, and a refractive index. May be a resin composition comprising a compound having a value of 1.35 to 1.60.
(C) Examples of the compound having two or more functional groups represented by the formula (1) in the molecule and having a refractive index of 1.35 to 1.60 include ethylene glycol diglycidyl ether, 1 , 4-butanediol diglycidyl ether, 1,2,7,8-diepoxyoctane, neopentyl glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol propoxylate tri Examples thereof include glycidyl ether and glycerol diglycidyl ether.

The relative dielectric constant of the inorganic particles used in the present invention is preferably 4.0 or more and 9.5 or less, and more preferably 4.0 or more and 9.0 or less.
Examples of the inorganic particles include silica particles such as colloidal silica, aerosil, and silica gel, glass particles mainly containing silicon oxide, or a mixture thereof.

  The refractive index of the inorganic particles is preferably 1.40 to 2.50, more preferably 1.43 to 2.20, and still more preferably 1.43 to 1.80.

The weight average particle diameter of the inorganic particles varies depending on the shape of the pattern to be formed, but is preferably 0.01 μm to 40 μm, more preferably 0.1 μm to 10 μm, still more preferably 0.1 μm to 5 μm. is there.
Moreover, you may mix and use the inorganic particle from which a weight average particle diameter differs in arbitrary ratios. Furthermore, the shape of the inorganic particles is not particularly limited, but is preferably spherical.

  The addition amount of the inorganic particles is a mass fraction with respect to the photosensitive paste, preferably 20 to 95% by mass, and more preferably 40 to 95% by mass.

Examples of the low melting point glass particles include tin oxide phosphate glass, bismuth oxide glass, and lead glass. The working temperature of the low-melting glass particles is usually 250 to 580 ° C.
Examples of the binder resin include butyral resin, polyvinyl alcohol, acrylic resin, poly α-methylstyrene, and the like.

The refractive index of the organic solvent contained in the photosensitive paste used in the present invention is preferably 1.4 to 1.8, more preferably 1.43 to 1.70, and particularly preferably 1.44. ~ 1.60.
Examples of the organic solvent include propylene glycol monobutyl ether, polypropylene glycol dibenzoate, 2-heptanone, propylene glycol monomethyl acetate, and gamma-butyrolactone.

The photosensitive paste used in the present invention may further contain boric acid or boron oxide.
When the boric acid or boron oxide is contained, the content thereof is a mass fraction with respect to the inorganic particles, preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass. Particularly preferred is 1 to 10% by weight.

Boric acid or boron oxide is preferably used after being supported or added to inorganic particles and then treated with a silane coupling agent.
As a loading method, after adding inorganic fine particles to a solution containing boric acid or boron oxide, the solvent is concentrated and dried, and after adding inorganic particles to a solution containing boric acid or boron oxide, boric acid is added. Alternatively, a method of crystallization with a solvent in which boron oxide or the like does not dissolve can be used.

As the silane coupling agent on the surface of the inorganic particles, a silane coupling agent such as vinyl, epoxy or oxetane is preferable.
Examples of the silane coupling agent include LS-70, LS-815, LS-2300, LS-4080, LS-2940, LS-3380, LS-4060, LS-1240, LS-1375, and LS-1260 (any Also, Shin-Etsu Chemical Co., Ltd.), TESOX (Toagosei Co., Ltd.) and the like can be mentioned.

The photosensitive paste used in the present invention may further contain a compound that generates an acid by electromagnetic radiation or heat, and a compound that generates an acid by electromagnetic radiation or heat together with the aforementioned boric acid or boron oxide. And may be contained.
Examples of the compound that generates an acid by electromagnetic radiation or heat include a photoacid generator, a photocationic polymerization initiator, and a thermal cationic polymerization initiator.
Examples of the photoacid generator include [cyclohexyl- (2-cyclohexanonyl) -methyl] sulfonium trifluoromethanesulfonate, bis (p-tolylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, tert-butylcarbonylmethyl- Tetrahydrothiophenium, trifluoromethanesulfonate and the like can be mentioned. As the photoacid generator, in addition to those described above, compounds described in JP-A No. 11-202495 can be used.
Examples of the photo cationic polymerization initiator and the thermal cationic polymerization initiator include iodonium salts, sulfonium salts, phosphate salts, and antimonate salts. Specific examples include Rhodosyl Photoinitiator 2074, Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172, and Adeka Opton CP series. In addition to the above, compounds described in JP-A-9-118663 can also be used.

  The addition amount of these photoacid generator, photocationic polymerization initiator, and thermal cationic polymerization initiator is a mass fraction with respect to the photosensitive paste, preferably 0.01 to 20% by mass, and more preferably 0.8. 05 to 10% by mass.

  In addition, the photosensitive paste used in the present invention may further contain a compound that generates an acid represented by the formula (9) by electromagnetic radiation, and the above-described boric acid or a derivative thereof, electromagnetic radiation or heat. You may use together with the compound which generate | occur | produces an acid, or these mixtures.

In Formula (9), Rf represents a C1-C20 monovalent organic group substituted with a fluorine atom.
Examples of the monovalent organic group having 1 to 20 carbon atoms substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group.
Examples of the compound that generates an acid represented by the formula (9) by electromagnetic radiation include an iodonium salt, a sulfonium salt, an ester compound, and the like made of the acid represented by the formula (9).
Examples of the iodonium salt include DPI-105, DPI-106 DPI-109, BI-105, MPI-105, MPI-109, BBI-105, BBI-109 (all manufactured by Midori Chemical).
Examples of the sulfonium salt include TPS-105, TPS-109, MDS-105, MDS-109, MDS-205, BDS-109, DTS-105, NDS-105, NDS-155, NDS-159, and NDS-165. (Both made by Midori Chemical).
Examples of ester compounds include NAI-105, NAI-109, NDI-105, NDI-109, SI-105, SI-109, PI-105, PI-109 (all manufactured by Midori Chemical). .

  The photosensitive paste used in the present invention comprises an alkali-soluble polyorganosiloxane resin composition and inorganic particles, and, if necessary, boric acid or a derivative thereof, a compound generating an acid by electromagnetic radiation or heat, and the above formula ( It can be produced by homogenously mixing and dispersing the compound represented by 9) that generates an acid, or a mixture of two or more of these with a three-roller or kneader.

Moreover, you may add the silicon compound of molecular weight 1000 or less which has a carboxyl group to the photosensitive paste used for this invention as needed.
Examples of the silicon compound having a molecular weight of 1000 or less include di (carboxypropyl) tetramethyldisiloxane.

Furthermore, the photosensitive paste used in the present invention includes at least one functional group selected from the group consisting of the functional group represented by the formula (1) or the functional group represented by the formula (2) as necessary. A silicon compound having a molecular weight of 1000 or less having a group may be added.
Examples of the silicon compound having a molecular weight of 1000 or less include glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane, oxetanyloxypropyltrimethoxysilane, oxetanyloxypropyltriethoxysilane, 1,3-bis (glycidyloxypropyl). ) -1,1,3,3, -tetramethyl-disiloxane, 1,3-dioxiranyl-1,1,3,3, -tetramethyl-disiloxane, 1,3-bis (oxetanyloxypropyl) -1 1,3,3, -tetramethyl-disiloxane and the like.
You may add additives, such as a light absorber, a photosensitizer, a plasticizer, a dispersing agent, a suspending agent, a leveling agent, to the photosensitive paste used for this invention as needed.

  As mentioned above, although embodiment of this invention was described, embodiment of the said disclosed invention is an illustration to the last, Comprising: The scope of the present invention is not limited to these embodiment. The scope of the present invention is defined by the terms of the claims, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

Production Example 1
Resin 1: Siloxane resin having phenolic hydroxyl group 187 g of tetraethoxysilane, 119 g of 2- (4′-t-butoxyphenyl) ethyl-dimethylchlorosilane (mixture of α adduct and β adduct), and 65 g of water in a mixture of 100 ml of ethanol Then, reaction was performed at 65 ° C. for 1 hour. Next, the reaction was continued for 11 hours while bubbling nitrogen through the reaction mixture to distill off ethanol. Further, 200 ml of methyl isobutyl ketone (MIBK) was added and reacted for 4.5 hours while distilling off ethanol and MIBK.
300 ml of MIBK was added to the reaction completed solution, and the mixture was washed with 300 ml of water three times until the aqueous layer became neutral.
After separating the aqueous layer, the organic layer was concentrated to obtain a viscous siloxane resin solution.
To the siloxane resin solution, 500 ml of 2-heptanone was added and partially concentrated to obtain a siloxane resin 2-heptanone solution. As a result of measuring solid content, it was 36.2%. As a result of GPC measurement, the weight average molecular weight in terms of polystyrene was 12,000.
Structural formula of siloxane resin having phenolic hydroxyl group:

Adjustment example 1
A uniform solution was prepared by putting 18.89 g of a 36.2% 2-heptanone solution of resin 1 obtained in Production Example 1, 6.84 g of polypropylene glycol dibenzoate, and 5.61 g of gamma-butyrolactone in a 100 ml eggplant flask. After 2-heptanone was distilled off and concentrated in the obtained solution using a rotary evaporator, 1,3-di (3′-carboxypropyl) -1,1,3,3-tetramethyl-disiloxane 0.21 g, Rhodesyl photoinitiator (PI-2074; manufactured by Rodel) 1.37 g and sensitizer (SP-100; manufactured by Asahi Denka Kogyo Co., Ltd.) 0.27 g were added, and 21.14 g of viscous photosensitivity. A composition was obtained.
21.14 g of the above alkali-soluble siloxane resin photosensitive composition, 1,3-bis (3′-glycidyloxypropyl) -1,1,3,3-tetramethyldisiloxane (manufactured by Shin-Etsu Chemical; LS-7970) 6.02 g, 77.29 g of spherical silica having a weight average particle size of 1.6 μm (manufactured by Admatex; SO-C5) and 19.49 g of lead-free low-melting glass (weight average particle size of 5 μm) are placed in a polypropylene sealed container and stirred. A uniform photosensitive paste was prepared by stirring using a defoamer (HM-500; manufactured by Keyence Corporation).

Example 1
The photosensitive paste prepared in Preparation Example 1 was applied once on a glass substrate using a 300 μm gap applicator. After coating, the coating film was prepared by drying in an oven at 130 ° C. for 30 minutes.
The glass substrate coated with the photosensitive paste is placed on a hot plate heated to 80 ° C. and left for 5 minutes. Subsequently, while maintaining the temperature of the hot plate at 80 ° C., using a chromium mask with a 40 μm line and 360 μm pitch, It exposed with the proximity exposure machine (MAP-1300; Dainippon Screen Mfg. Co., Ltd. product). The irradiation exposure dose was 600 mJ / cm ² .
After the exposure, it was baked on a hot plate at 130 ° C. for 10 minutes, and then developed with a 1% by mass aqueous sodium hydroxide solution. A pattern having a top width of 55 μm, a bottom width of 180 μm, and a height of 153 μm was obtained without peeling.

Comparative Example 1
A coating film was prepared in the same manner as in Example 1 using the photosensitive paste prepared in Preparation Example 1.
The substrate was kept at room temperature (25 ° C.) without being heated and exposed in the same manner as in Example 1. The irradiation exposure dose was 800 mJ / cm ² .
After the exposure, the substrate was baked on a hot plate at 130 ° C. for 10 minutes, and developed with a 1% by mass aqueous sodium hydroxide solution. A pattern having a top width of 103 μm, a bottom width of 185 μm, and a height of 130 μm was obtained without peeling.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the manufacturing method which can reduce the exposure amount at the time of the partition pattern formation which is a display member using a photosensitive paste, and shortens exposure time.

Claims (10)

  It consists of a step of applying and drying a photosensitive paste containing inorganic particles on a substrate, a step of exposing using a mask, a step of developing an unexposed portion, and a step of firing a pattern obtained after development. In the partition wall forming method, a method for forming a display member in which a substrate is heated to 40 ° C. to 150 ° C. in a step of exposing using a mask.   The formation method according to claim 1, wherein the inorganic particles have a relative dielectric constant of 4.0 or more and 9.5 or less.   The formation method according to claim 1 or 2, wherein the inorganic particles are at least one inorganic particle selected from the group consisting of silica particles and glass particles.   The forming method according to claim 1, wherein the photosensitive paste contains an alkali-soluble polyorganosiloxane resin composition. The forming method according to claim 4, wherein the alkali-soluble polyorganosiloxane resin composition contains the following formulas (A) and (B).
(A) a polyorganosiloxane resin having at least one functional group selected from the group consisting of a functional group represented by formula (1) and a functional group represented by formula (2) (B) a polyorgano having a hydroxyl group Siloxane resin

[In Formula (1) and Formula (2), A ¹ and A ² each independently represents an oxygen atom or a sulfur atom.
^{R a, R b, R '} a and ^{R' b} independently represent a divalent organic group.
R ^{1 to} R ⁸ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
l ₁ , m ₁ , l ₂ , and m ₂ each independently represents an integer of 0 or more and 20 or less. ] (B) The forming method according to claim 4 or 5, wherein the polyorganosiloxane resin having a hydroxyl group is a resin having a phenolic hydroxyl group represented by the formula (3).

Wherein (3), A ³ represents an oxygen atom or a sulfur atom.
R ^{″ a} and R ^{″ b} each independently represents a divalent organic group.
R ^{9 to} R ¹² each independently represent a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 20 carbon atoms.
l ₃ and m ₃ each independently represents an integer of 0 or more and 20 or less. ] (B) The forming method according to claim 4 or 5, wherein the polyorganosiloxane resin having a hydroxyl group is a resin having a hydroxyl group represented by the formula (4).

[In Formula (4), R < ¹³ > -R < ¹⁸ > represents a hydrogen atom or a C1-C20 monovalent organic group each independently.
p and q each independently represents an integer of 0 or more and 20 or less.
r represents an integer of 1 or more and 20 or less. ]   The alkali-soluble polyorganosiloxane resin composition is represented by (B) a polyorganosiloxane resin having a hydroxyl group according to claim 5, and (C) two or more formulas (1) according to claim 5 in the molecule. The forming method according to claim 4, comprising a functional group having a refractive index of 1.35 to 1.60.   The forming method according to claim 1, wherein the inorganic particles have a refractive index of 1.40 to 2.50. An exposure machine comprising a heating device used in the forming method according to claim 1.