JP2008070416A - Pattern formation method - Google Patents

Abstract

The present invention provides a method for manufacturing a partition using a photosensitive paste, which can form a pattern with a low exposure (high sensitivity) even with a thick film, and has excellent productivity. Each step;
A photosensitive paste containing (I) (A) inorganic particles, (B) an alkali-soluble resin, (C) a crosslinking agent, (D) an acid generator and (E) an organic solvent is applied onto the substrate, A step of obtaining a coating film,
(II) a step of removing the organic solvent remaining in the coating film obtained by the step (I) (III) a step of exposing the coating film on the substrate obtained by the step (II),
(IV) A step of heating the coating film exposed in step (III) at 80 ° C. to 160 ° C. for 3 minutes to 60 minutes and then cooling to room temperature,
(V) A step of developing the coating film obtained in step (IV) to form a pattern on the substrate,
(VI) Provided is a pattern forming method including a step of baking the pattern obtained in the step (V) together with a substrate at a temperature of 450 ° C. to 600 ° C.
[Selection figure] None

Description

  The present invention relates to a photosensitive paste. More specifically, the present invention relates to a photosensitive paste suitable for forming partition walls on a plasma display back plate.

  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 that is a member of a plasma display.

  Examples of the photosensitive paste that forms the partition walls so far include a photosensitive paste containing acrylic acid-styrene copolymer, glass powder, and a photopolymerization initiator, and the photosensitive paste is placed on a substrate. A method is known in which a barrier rib pattern is formed by coating, exposing and developing, followed by baking to form barrier ribs (see, for example, Patent Document 1).

Japanese Patent Laid-Open No. 2001-22064

In the partition forming method using the photosensitive paste of Patent Document 1, since the sensitivity in the lithography process is controlled by the generation of radicals of the photopolymerization initiator, there is a problem that the sensitivity is easily deteriorated and the productivity is lowered. In addition, since radicals generated from the photopolymerization initiator are easily deactivated by oxygen in the air, there is a problem that the atmosphere control during exposure becomes complicated. Also, such a problem tends to become more prominent when attempting to obtain a thick film partition.
An object of the present invention is to provide a method of manufacturing a partition wall that is capable of forming a pattern with a low exposure amount even with a thick film and has excellent productivity that can achieve a highly sensitive lithography process. Furthermore, the partition obtained by the manufacturing method can be suitably used as a member for plasma display.

  The present inventor has intensively studied a lithography process using a photosensitive paste in a method for manufacturing a partition wall that can solve the above-mentioned problems, and has completed the present invention.

That is, the present invention provides the following [1] and [2].
[1] Each step;
A photosensitive paste containing (I) (A) inorganic particles, (B) an alkali-soluble resin, (C) a crosslinking agent, (D) an acid generator and (E) an organic solvent is applied onto the substrate, A step of obtaining a coating film,
(II) a step of removing the organic solvent remaining in the coating film obtained by the step (I) (III) a step of exposing the coating film on the substrate obtained by the step (II),
(IV) A step of heating the coating film exposed in step (III) at 80 ° C. to 160 ° C. for 3 minutes to 60 minutes and then cooling to room temperature,
(V) A step of developing the coating film obtained in step (IV) to form a pattern on the substrate,
(VI) A pattern forming method [2] characterized in that it comprises a step of firing the pattern obtained in step (V) together with the substrate at a temperature of 450 ° C. to 600 ° C. Is a step of removing the organic solvent remaining in the coating film by heating to 70 to 140 ° C. for 5 to 60 minutes and then cooling to room temperature [1] ] Pattern formation method

  In addition to the problems related to radical deactivation as described above, the photopolymerization initiator used in the conventional photosensitive paste performs photocuring of the binder resin in the photosensitive paste by the radical. In the lithography process, the sensitivity is likely to be lowered, and particularly when the coating film obtained from the photosensitive paste is a thick film, the knowledge that the sensitivity is remarkably deteriorated was obtained. In accordance with such knowledge, the photosensitive component of the photosensitive paste is used as an acid generator, and by performing the above heat treatment after exposure or before and after exposure, it has been found that a pattern can be formed with high sensitivity even with a thick film. .

（式中、Ｑ₂、Ｑ₃は、それぞれ独立に式（４）で表される基であり、Ｑ₁は式（５ａ）または式（５ｂ）で示される２価の基を表す。）

（式中、Ｔ₁は炭素数１〜６のアルキレン基、炭素数１〜６のアルキレンオキシアルキレン基またはフェニレン基を表す。ｍは０または１である。）

（式中、Ｔ₂〜Ｔ₇は、メチル基またはフェニル基を表す。Ｔ₈は酸素原子、メチレン基、エテニレン基、エチニレン基、フェニレン基、ナフタレンジイル基およびビフェニルジイル基からなる群から選ばれる。）
［８］前記（Ａ）が、軟化点が４００℃〜６００℃である低融点ガラス粒子を含む無機粒子である［１］〜［７］のいずれかのパターン形成方法
［９］前記感光性ペーストにおける、前記（Ａ）〜（Ｅ）の含有比率が、それぞれ（Ａ）２０〜９５質量％、（Ｂ）２〜３０質量％、（Ｃ）１〜３０質量％、（Ｄ）０.０１〜２０質量％および（Ｅ）１〜４０質量％である［１］〜［８］のいずれかのパターン形成方法 Furthermore, the present invention provides the following [3] to [9] as suitable photosensitive pastes applied to [1] or [2].
[3] The pattern forming method of [1] or [2], wherein (E) comprises an organic solvent (Ea) having a boiling point at 1 atm of 100 ° C. or higher and lower than 195 ° C. as an essential component [ 4] The pattern formation method of [3], wherein the organic solvent (Ea) is 70% by mass or more when the total amount of (E) is 100% by mass [5] The organic solvent ( E-a) is ethylene glycol diacetate [3] or [4] pattern formation method [6] All organic solvents constituting the above (E) have a refractive index of 1.40 at 25 ° C. 1. The pattern forming method according to any one of [1] to [5], which is an organic solvent of 1.80 [7] The (B) alkali-soluble resin is a novolac resin and / or a novolac resin derivative, and the (C) crosslinking agent Is represented by the following formula (3) An epoxy group silicon compound, any pattern forming method [1] to [5]

(In the formula, Q ₂ and Q ₃ are each independently a group represented by the formula (4), and Q ₁ represents a divalent group represented by the formula (5a) or the formula (5b).)

(In the formula, T ₁ represents an alkylene group having 1 to 6 carbon atoms, an alkyleneoxyalkylene group having 1 to 6 carbon atoms, or a phenylene group. M is 0 or 1.)

(Wherein T _{2 to} T ₇ represent a methyl group or a phenyl group. T ₈ is selected from the group consisting of an oxygen atom, a methylene group, an ethenylene group, an ethynylene group, a phenylene group, a naphthalenediyl group, and a biphenyldiyl group. .)
[8] The pattern forming method according to any one of [1] to [7], wherein (A) is an inorganic particle containing low-melting glass particles having a softening point of 400 ° C to 600 ° C [9] The photosensitive paste The content ratios of (A) to (E) are (A) 20 to 95% by mass, (B) 2 to 30% by mass, (C) 1 to 30% by mass, and (D) 0.01 to The pattern forming method according to any one of [1] to [8], which is 20% by mass and (E) 1 to 40% by mass

The present invention also provides the following [10] to [12] using any one of the pattern forming methods.
[10] Plasma display panel [11] [11] plasma display panel partition comprising plasma display panel partition [11] [10] plasma display panel partition manufactured using the pattern forming method according to any one of the above Display panel with components

  According to the pattern forming method of the present invention, even a thick film exceeding 50 μm can be formed with a single low exposure dose, and the partition for plasma display can be produced with high productivity. is there.

Hereinafter, preferred embodiments of the present invention will be described.

  The photosensitive paste applied to the present invention will be described. The said photosensitive paste contains said (A)-(E).

  First, (A) inorganic particles will be described. The inorganic particles are not particularly limited as long as they are general. That is, inorganic particles made of glass, ceramics (silica, alumina, cordierite, etc.), metals (gold, platinum, silver, copper, nickel, palladium, tungsten, ruthenium oxide, alloys thereof, etc.) can be used. Inorganic particles made of glass or ceramics containing silicon oxide, boron oxide or aluminum oxide as essential components are preferred. These are insulators and are preferably used for forming an insulating pattern, particularly for forming a partition wall of a plasma display or a plasma addressed liquid crystal display.

  Preferred inorganic particles in (A) are those having a relative dielectric constant of 4.0 or more and 9.5 or less, more preferably 4.0 or more and 9.0 or less at a measurement temperature of 20 ° C. . It is preferable that the relative dielectric constant is in the above-mentioned range since reactive power when driving as a plasma display panel is reduced. Here, the relative dielectric constant can be measured using a commercially available bridge-type dielectric constant measuring device (for example, model number TR-10C manufactured by Ando Electric Co., Ltd. can be mentioned).

  Moreover, as a suitable inorganic particle in (A), the refractive index is the range of 1.40-2.50 in measurement temperature 25 degreeC, More preferably, it is the range of 1.43-2.20, Especially preferably, it is the range of 1.43-1.80. It is preferable to use inorganic particles having a refractive index in the above range as (A) because there is a tendency that a good pattern can be formed because light scattering is small during exposure. The refractive index can be measured using a commercially available prism refractive index measuring device (for example, model number GP1-P manufactured by OPTEC).

  Furthermore, as an inorganic particle applied to (A), the volume average particle diameter at a measurement temperature of 25 ° C. is preferably 0.01 to 40 μm, more preferably 0.1 to 10 μm, and 1 to 8 μm. Particularly preferred. When the volume average particle size is in the above range, the amount of inorganic particles filled in the partition formed using the photosensitive paste can be increased, so that a partition with less shrinkage during firing can be easily obtained. In view of this, it is preferable because the scattering of light during exposure is small and a good pattern tends to be formed. The volume average particle diameter can be measured using a commercially available light scattering particle diameter measuring apparatus (for example, model number DLS-7000 manufactured by Otsuka Electronics Co., Ltd.).

  In the photosensitive paste of the present invention, inorganic particles having different volume average particle diameters may be mixed at an arbitrary ratio and used as (A).

  The shape of the inorganic particles is not particularly limited, and may be crushed or spherical, but is preferably spherical.

  Inorganic particles particularly suitable as (A) include, for example, silica particles derived from colloidal silica, silica particles such as aerosil and silica gel, low-melting glass particles having a softening point of 400 ° C. to 600 ° C., or a softening temperature of 601 ° C. or higher. Glass particles, or a mixture thereof. In particular, a photosensitive paste containing inorganic particles containing low-melting glass particles as (A) is preferable because the strength of partition walls obtained by the method described later is high. Here, examples of the low melting point glass particles include glass particles made of zinc oxide glass, tin oxide phosphate glass, bismuth oxide glass, lead glass, and the like.

The addition ratio of (A) used in the photosensitive paste of the present invention is preferably 20 to 95% by mass, more preferably 40 to 95% by mass, based on the total amount of the photosensitive paste.
When the addition ratio of (A) is in the above range, the film shrinkage during firing tends to be small and it tends to be difficult to peel off from the substrate, and the light scattering during exposure tends to be small and a good pattern can be formed. Is preferable.

Next, (B) the alkali-soluble resin will be described.
Here, the notation of “alkali-soluble” means that it can be dissolved in either an alkaline aqueous solution, an organic solvent exhibiting alkalinity, or an organic solvent-water mixed solution exhibiting alkalinity. Examples of the alkali-soluble group that exhibits such alkali-solubility include a carboxyl group (—COOH), a phenolic hydroxyl group, a phosphonic acid group (—PO ₃ H ₂ ), a sulfonic acid group (—SO ₃ H), and a sulfonic imide group (— SO ₂ NHSO ₂ —) is at least one acid group selected from the group consisting of carboxylic acid anhydride groups, groups in which phenolic hydroxyl groups are protected by esterification or etherification, and the like. Mention may be made of groups which are converted into groups. As the resin having an alkali-soluble group, known resins can be used. For example, novolak resins and derivatives thereof, styrene-maleic anhydride copolymers, polyvinylhydroxybenzoates and derivatives thereof, polyhydroxystyrene and derivatives thereof, Examples include carboxyl group-containing acrylic resins and derivatives thereof, polystyrene sulfonic acid and derivatives thereof, and the like.

（式中、ｎは０以上２以下の整数を表わす。Ｒ₁は炭素数１〜２０の一価の有機基を表し、ｎが２の場合は、２つあるＲ₁は同一あるいは異なっていてもよい。） Among the alkali-soluble resins exemplified above, suitable alkali-soluble resins applied to (B) of the present invention are novolak resins and / or novolak resin derivatives. Specifically, the following (a) and (b) It is preferable that it is 1 type or 2 types or more selected from these.
The “novolak resin derivative” means that some phenolic hydroxyl groups in the novolac resin are protected with an alkoxy group, an acyl group, etc. In the present invention, as shown in the following (b), A novolak resin derivative having a group is preferred.

(A) A novolak resin obtained by polycondensation of a phenol compound represented by formula (1) and an aldehyde compound represented by formula (2)

(In the formula, n represents an integer of 0 or more and 2 or less. R ₁ represents a monovalent organic group having 1 to 20 carbon atoms. When n is 2, two R _{1 s} are the same or different. May be good.)

（式中、Ｒ₂は、水素原子または炭素数１〜２０の一価の有機基を表す）
（ｂ）ノボラック樹脂（ａ）のフェノール性水酸基の一部をＯＲ₃基に置換されてなる樹脂（ここで、Ｒ₃は炭素数１〜２０の一価の有機基である）

(Wherein R ₂ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)
(B) A resin obtained by substituting a part of the phenolic hydroxyl group of the novolak resin (a) with an OR ₃ group (where R ₃ is a monovalent organic group having 1 to 20 carbon atoms)

(A) is a novolak resin obtained by polycondensation of the phenol compound represented by the above formula (1) and the aldehyde compound represented by the formula (2), wherein R ₁ in the formula (1) is the number of carbon atoms. 1 to 20 monovalent organic groups are represented. The monovalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and examples thereof include a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms and 3 to 20 carbon atoms. A branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like. The aromatic hydrocarbon group having 6 to 20 carbon atoms 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 methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl. Group, undecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like, in particular, methyl group, ethyl group, propyl group, butyl group, pentyl group, A hexyl group is preferred.

  Examples of the branched aliphatic hydrocarbon group having 3 to 20 carbon atoms include isopropyl group, isobutyl group, tertiary butyl group, tertiary octyl group, and the like, and isopropyl group and isobutyl group are particularly preferable.

  Examples of the cycloaliphatic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. In particular, a cyclopentyl group and a cyclohexyl group are exemplified. preferable.

  The aromatic hydrocarbon group having 6 to 20 carbon atoms has an aromatic ring and the total number of carbon atoms constituting the group is 6 to 20. Examples of aromatic ring substituents include alkyl groups such as methyl, ethyl, propyl, and butyl groups, alkenyl groups such as allyl groups and vinyl groups, alkenyloxy groups such as allyloxy groups, and ethynyl groups. Alkynyloxy groups, such as an alkynyl group and an ethynyloxy group, are mentioned.

  Specific examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, propylphenyl group, butylphenyl. Group, methyl naphthyl group, dimethyl naphthyl group, trimethyl naphthyl group, vinyl naphthyl group, methyl anthryl group, ethyl anthryl group and the like, and phenyl group, tolyl group and xylyl group are particularly preferable.

The substitution position of R ₁ in the formula (1) is preferably _one in which at least two positions are not substituted among the 2-position, 4-position, and 6-position from the phenol hydroxyl group. Specific examples include phenol (hydroxybenzene), o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-propylphenol, m-propylphenol, p-propylphenol, o-isopropylphenol, m-isopropyl Phenol, p-isopropylphenol, o-tert-butylphenol, m-tertiarybutylphenol, o-hexylphenol, m-hexylphenol, o-decylphenol, m-decylphenol, o-dodecylphenol, m-dodecylphenol, o -Hexadeci Ruphenol, m-hexadecylphenol, o-icosylphenol, m-icosylphenol, o-cyclopentylphenol, m-cyclopentylphenol, o-cyclohexylphenol, m-cyclohexylphenol, o-cycloheptylphenol, m-cyclo Heptylphenol, o-phenylphenol, m-phenylphenol, o-toluylphenol, m-toluylphenol, o-naphthylphenol, m-naphthylphenol,
2,5-xylenol, 2,3-xylenol, 3,5-xylenol, 2-ethyl-5-methylphenol, 2-ethyl-3-methylphenol, 3-ethyl-5-methylphenol, 2-isopropyl-5 -Methylphenol, 2-isopropyl-3-methylphenol, 3-isopropyl-5-methylphenol, 2-tertiarybutyl-5-methylphenol, 2-tertiarybutyl-3-methylphenol, 3-tertiarybutyl- 5-methylphenol, 2-hexyl-5-methylphenol, 2-hexyl-3-methylphenol, 3-hexyl-5-methylphenol, 2-cyclohexyl-5-methylphenol, 2-cyclohexyl-3-methylphenol, 3-cyclohexyl-5-methylphenol, 2-phenyl Nyl-5-methylphenol, 2-phenyl-3-methylphenol, 3-phenyl-5-methylphenol, 2-naphthyl-5-methylphenol, 2-naphthyl-3-methylphenol, 3-naphthyl-5-methyl Phenol, 2,5-diethylphenol, 2,3-diethylphenol, 3,5-diethylphenol, 2,5-dipropylphenol, 2,3-dipropylphenol, 3,5-dipropylphenol, 2,5 -Biscyclohexylphenol, 2,3-biscyclohexylphenol, 3,5-biscyclohexylphenol, 2,5-diphenylphenol, 2,3-diphenylphenol, 3,5-diphenylphenol and the like.
In particular, phenol (hydroxybenzene), o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3-xylenol, 2-butylphenol, 2-isobutylphenol, 2-cyclohexyl Phenol and 2-phenylphenol are preferable, and phenol (hydroxybenzene), o-cresol, m-cresol, and p-cresol are particularly preferable.

The R ₂ group in the formula (2) is selected from a hydrogen atom and a monovalent organic group having 1 to 20 carbon atoms, and examples of the monovalent organic group include those equivalent to the R ₁ group. Specific examples of the aldehyde compound represented by the formula (2) include formaldehyde, acetaldehyde, propanal, butanal, hexanal, octanal, decanal, dodecanal, hexadecanal, icosanal, 2-methylpropanal, 2-methylbutanal. 2-ethylbutanal, 2,2-dimethylpropanal, acrolein, 2-butenal, 2-hexenal, 2-octenal, acetylenaldehyde, 2-butynal, 2-hexinal, 2-octynal, cycloheptylcarbalaldehyde, Examples include cyclohexyl carbaldehyde, benzaldehyde, 1-naphthyl aldehyde, 2-naphthyl aldehyde, styryl aldehyde, and the like. As the aldehyde compound, a depolymerizable polymer compound can be used, and the aldehyde group may be protected with an acetal group or a hemiacetal group.

  Among the aldehyde compounds represented by the formula (2), formaldehyde and acetaldehyde are particularly preferable, and formaldehyde is particularly preferable. As formaldehyde, paraformaldehyde, which is a depolymerizable polymer compound, or formalin, which is an aqueous solution, can also be used.

  The polycondensation method of the compound represented by the formula (1) and the aldehyde compound represented by the formula (2) is not particularly limited. For example, an acid catalyst or an alkali catalyst is used in the presence or absence of a reaction solvent. Can be achieved. The reaction temperature is 0 to 200 ° C., preferably 50 to 150 ° C., and the reaction time is 0.1 to 30 hours, preferably 1 to 20 hours. Examples of the acid catalyst include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, malonic acid, and toluenesulfonic acid. Examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, and carbonate. Examples thereof include sodium hydrogen, ammonia, tetramethylammonium hydroxide, triethylamine, morpholine, pyridine and the like.

  Reaction solvents used for polycondensation include alcohols such as methanol, ethanol, isopropanol, and tertiary butyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl hexyl ketone, methyl heptyl ketone, and cyclohexyl ketone; propyl acetate, butyl acetate , Esters such as isobutyl acetate, methyl propionate, ethyl lactate, propylene glycol acetate; ethers such as dibutyl ether, tetrahydrofuran, tetrahydropyran, dioxane; aromatic hydrocarbons such as benzene, toluene, xylene; dichloromethane, chloroform, Halogenated hydrocarbons such as carbon tetrachloride and bromoform; hydrocarbons such as hexane, heptane, decane, and petroleum ether can be used. It can be used as a mixture of the above. In addition, water may coexist in the reaction system, and in the case of a solvent that is incompatible with water, a reaction solvent separated into two layers may be used. Water may be removed by distillation dehydration or the like.

  In the above polycondensation method, ketones, esters, aromatic hydrocarbons are used as reaction solvents, organic acids such as acetic acid, oxalic acid, malonic acid, toluenesulfonic acid, or ammonia, tetramethylammonium hydroxide, It is preferable to use an alkali such as triethylamine as a catalyst. The catalyst may or may not dissolve in the reaction solvent used.

(B) is obtained by substituting a part of the phenolic hydroxyl group of the novolak resin (a) obtained as described above with an OR ₃ group. Here, R ₃ radical is a monovalent organic group having 1 to 20 carbon atoms include the same examples as R ₁ or R ₂ described above.

Examples of the reaction for replacing the phenolic hydroxyl group with an OR ₃ group include strong alkalis such as sodium hydroxide, potassium hydroxide, metallic sodium, metallic lithium, metallic potassium, n-butyllithium, sodium naphthalate, and sodium methoxide. It can be used by converting the phenolic hydroxyl group into a metal phenolate group and reacting the compound represented by the formula (6).

（式中、Ｒ₃は前記と同等の定義である。Ｔはフッ素原子、塩素原子、臭素原子、ヨウ素原子、メシル基又はトシル基からなる群から選ばれる。）
式（６）で示される化合物は、使用するノボラック樹脂（ａ）のフェノール性水酸基１モル当量に対して、０．９９モル当量以下、好ましくは０．８モル当量以下、特に好ましくは０．５モル当量以下を使用する。
ここで、使用するノボラック樹脂（ａ）中のフェノール性水酸基のモル当量は、アルカリ滴定法を用いて求めることができる。

(In the formula, R ₃ has the same definition as above. T is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyl group or a tosyl group.)
The compound represented by the formula (6) is 0.99 molar equivalent or less, preferably 0.8 molar equivalent or less, particularly preferably 0.5 molar equivalent to 1 molar equivalent of the phenolic hydroxyl group of the novolak resin (a) to be used. Use molar equivalents or less.
Here, the molar equivalent of the phenolic hydroxyl group in the novolak resin (a) to be used can be determined using an alkali titration method.

  Specific examples of the compound represented by the formula (6) are methyl fluoride, ethyl fluoride, decyl fluoride, hexyl fluoride, octyl fluoride, dodecyl fluoride, hexadecyl fluoride, icosyl fluoride, methyl chloride, ethyl chloride. , Decyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, hexadecyl chloride, icosyl chloride, methyl bromide, ethyl bromide, decyl bromide, hexyl bromide, octyl bromide, dodecyl bromide, hexadecyl bromide, icosyl bromide , Benzyl bromide, methyl iodide, ethyl iodide, decyl iodide, hexyl iodide, octyl iodide, dodecyl iodide, hexadecyl iodide, icosyl iodide, benzyl iodide, methyl ethyl sulfonate, methyl butyl sulfonate , Methyl octyl sulfonate, methyl decyl sulfonate, toluyl ethyl sulfonate, buty Acid toluyl, octyl sulfonic acid toluyl, cited toluic decyl sulfonate and the like, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide are preferred.

  Examples of the reaction solvent include alcohols such as methanol, ethanol, isopropanol, and tertiary butyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl hexyl ketone, methyl heptyl ketone, and cyclohexyl ketone; dibutyl ether, tetrahydrofuran, tetrahydropyran, and dioxane. Ethers such as benzene, toluene, xylene, etc .; hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, bromoform; hydrocarbons such as hexane, heptane, decane, petroleum ether, etc. These may be used alone or in combination of two or more. In particular, ethers, aromatic hydrocarbons or halogenated hydrocarbons are preferred. In the reaction, water may coexist as long as the reactant used is not deactivated, but a dehydrated solvent having a water content of 100 ppm or less is preferred. The reaction temperature is 0.1 to 20 hours, preferably 1 to 10 hours, and the reaction temperature is −60 to 100 ° C., preferably −20 to 50 ° C.

In particular, (B) of the present invention is particularly preferably a phenol novolak resin or a cresol novolak resin obtained by polymerizing formaldehyde with a compound in which R ₁ in formula (1) is a hydrogen atom or a methyl group. Phenol novolac resins or cresol novolac resins can be preferably used because of high dissolution contrast. Moreover, the addition ratio of (B) used for the photosensitive paste of this invention becomes like this. Preferably it is 2-30 mass% with respect to the photosensitive paste whole quantity, More preferably, it is 3-20 mass%.

  The alkali-soluble resin obtained as described above contains the catalyst or catalyst residue used in the condensation reaction or substitution reaction, the unreacted phenol compound represented by the formula (1), and the unreacted aldehyde represented by the formula (2). It is preferable to remove the compound or the unreacted compound represented by the formula (6) by a known method. The reaction solvent used in the condensation reaction or the substitution reaction can also be removed by a known method. However, when a solvent applicable to the organic solvent (E) described later is used, the reaction solvent is not removed. You may use for adjustment of the photosensitive paste as a solution which melt | dissolved soluble resin.

  The polystyrene-reduced weight average molecular weight of the alkali-soluble resin (B) by GPC method is preferably 350 to 30,000, more preferably 350 to 10,000. When the weight average molecular weight is in the above range, the curability of the exposed area tends to be high, the solubility of the unexposed area tends to be high, and the pattern formation characteristics tend to be favorable, which is preferable.

  The addition ratio of (B) used for the photosensitive paste of this invention becomes like this. Preferably it is 1-30 mass% with respect to the photosensitive paste whole quantity, More preferably, it is 5-20 mass%.

（式中、Ｑ₂、Ｑ₃は、それぞれ独立に式（４）で表される基であり、Ｑ₁は式（５ａ）または式（５ｂ）で示される２価の基を表す。） Next, the crosslinking agent (C) will be described.
As the crosslinking agent (C), an epoxy-containing silicon compound represented by the formula (3) is suitable. Since such an epoxy-containing silicon compound is less likely to volatilize in heat treatment before and after exposure, it effectively causes a crosslinking reaction with the (B) by exposure and has a low viscosity, so that the photosensitive paste itself is thickened. There is an advantage that the operability is not deteriorated.

(In the formula, Q ₂ and Q ₃ are each independently a group represented by the formula (4), and Q ₁ represents a divalent group represented by the formula (5a) or the formula (5b).)

（式中、Ｔ₁は炭素数１〜６のアルキレン基、炭素数１〜６のアルキレンオキシアルキレン基またはフェニレン基を表す。ｍは０または１である。）

(In the formula, T ₁ represents an alkylene group having 1 to 6 carbon atoms, an alkyleneoxyalkylene group having 1 to 6 carbon atoms, or a phenylene group. M is 0 or 1.)

（式中、Ｔ₂〜Ｔ₇は、メチル基又はフェニル基を表す。Ｔ₈は酸素原子、メチレン基、エテニレン基、エチニレン基、フェニレン基、ナフタレンジイル基およびビフェニルジイル基からなる群から選ばれる。）

(Wherein T _{2 to} T ₇ represent a methyl group or a phenyl group. T ₈ is selected from the group consisting of an oxygen atom, a methylene group, an ethenylene group, an ethynylene group, a phenylene group, a naphthalenediyl group, and a biphenyldiyl group. .)

Here, Q ₂ and Q ₃ each independently represent a group having an epoxy group or an oxetane group represented by the formula (4). Here, when T ₁ is an alkylene group, examples thereof include glycidyl group, 1,2-epoxybutyl group, 1,2-epoxyhexyl group, and when alkylene group is alkyleneoxyalkylene group, glycidyloxyethyl group, glycidyloxy Examples include a propyl group, a glycidyloxybutyl group, a 1,3-epoxybutyl group, and a 1,3-epoxyhexyl group. When T ₁ is a phenylene group, a 1,2-epoxyethylphenyl group and a 1,3-epoxypropylphenyl group are exemplified. In particular, the case where T ₁ is an alkyleneoxyalkylene group is preferable since it is simple in production, and a glycidyloxypropyl group is particularly preferable.
Q ₁ is a divalent group having one or two silicon atoms represented by formula (5a) or formula (5b), and is a dimethylsilanediyl group, diphenylsilanediyl group, 1,1,3,3- Tetramethyldisiloxanediyl group, 1,1,3,3-tetraphenyldisiloxanediyl group, 1,1,3,3-tetramethyldisilamethylenediyl group, phenylenebis (dimethylsilylene) group, etc. A 1,1,3,3-tetramethyldisiloxanediyl group is particularly preferred.
(C) is particularly preferably 1,3-di (3′-glycidyloxypropyl) -1,1,3,3, -tetramethyldisiloxane.
1,3-di (3′-glycidyloxypropyl) -1,1,3,3, -tetramethyldisiloxane is commercially available for use as an epoxy resin modifier and is readily available. is there.

  The addition ratio of (C) used in the photosensitive paste of the present invention is preferably 1 to 30% by mass and more preferably 1 to 20% by mass with respect to the total amount of the photosensitive paste.

Next, (D) the acid generator will be described.
Examples of (D) include a photoacid generator and a photocationic polymerization initiator.

  Examples of the photoacid generator include [cyclohexyl- (2-cyclohexanonyl) -methyl] sulfonium trifluoromethanesulfonate, bis (p-tolylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and tertiary butylcarbonylmethyl. -Tetrahydrothiophenium trifluoromethane sulfonate etc. are mentioned. In addition to these, compounds described in JP-A-11-202495 can be used as the photoacid generator.

  Examples of the photocationic polymerization initiator include iodonium salts, sulfonium salts, phosphate salts, and antimonate salts. Specifically, Rhodesyl Photoinitiator 2074 (manufactured by Rodel), Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172 (all Asahi Denka Kogyo) Etc.). In addition to these, compounds described in JP-A-9-118663 can also be used.

Content of (D) with respect to the photosensitive paste applied to this invention becomes like this. Preferably it is 0.01-20 mass% with respect to the photosensitive paste whole quantity, More preferably, it is 0.05-10 mass%.
When the content of (D) is in the above range, there is a tendency that a pattern can be formed with good productivity, which is preferable.

  Next, (E) will be described. (E) can be selected within a range in which the viscosity of the photosensitive paste can be adjusted and the operability such as coating can be improved. In particular, it includes an organic solvent (EA) having a boiling point at 1 atm of 100 ° C. or more and less than 195 ° C. The inventors of the present invention have found that the obtained partition wall has significantly improved adhesion to the substrate.

Specifically, (EA) will be described. (EA) can be selected in consideration of the boiling point at 1 atm. Specifically, for example, a known document such as a solvent handbook (Asahara Teruzo, Senao Manabu et al., Kodansha, 1976) ) Etc., a suitable solvent can be easily selected from the boiling point data.
Specific examples of suitable organic solvents include dipropylene glycol methyl ether (boiling point 190 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), ethylene glycol diacetate (boiling point 186 ° C), ethylene glycol monoacetate (boiling point 187 ° C). ), Ethylene glycol monomethyl ether (boiling point 194 ° C.) and the like. Among these, it is preferable to use ethylene glycol diacetate as (EA) from the viewpoint of the transparency of the coating film obtained by applying the photosensitive paste.

  Further, all the organic solvents constituting (E) are preferably organic solvents having a refractive index of 1.40 to 1.80 at 25 ° C., and further, organic solvents having a refractive index of 1.41 to 1.70. In particular, an organic solvent having a refractive index of 1.42 to 1.60 is preferable. When the refractive index of the solvent is in the above range, the transparency of the photosensitive paste after film formation tends to be high, which is preferable. The refractive index of the organic solvent can be measured at a measurement temperature of 25 ° C. using a refractometer (for example, RA-520N manufactured by Kyoto Electronics Industry Co., Ltd.). In addition, the refractive index, for example, using values described in documents such as Revised 4th edition, Chemical Handbook, Fundamentals II, pages 514-520 (edited by the Chemical Society of Japan, Maruzen Co., Ltd., issued on September 30, 1993). A suitable one can also be selected.

  Specifically, organic solvents having a refractive index of 1.40 to 1.80 include gamma-butyrolactone (refractive index 1.44) and 1,2-propanediol dibenzoate (refractive index 1.54). In addition, ethylene glycol diacetate exemplified as the organic solvent (EA) is a particularly preferable organic solvent as (E) because its refractive index is 1.42.

  As content of (E) in the photosensitive paste applied to this invention, it is 1-40 mass% normally with respect to the photosensitive paste whole quantity, Preferably it is 3-30 mass%, More preferably, it is 5 ˜20 mass%.

  Furthermore, additives such as a light absorber, a photosensitizer, a plasticizer, a dispersant, a suspending agent, and a surfactant may be added to the photosensitive paste applied to the present invention as necessary. .

Next, the pattern forming method of the present invention will be described.
The pattern formation method of this invention is a pattern formation method which has each process which consists of said (I)-(VI).

  First, (I) will be described. A photosensitive paste is applied on the entire surface of the substrate or partially applied to form a coating film. As the coating method, for example, any coating method such as a bar coater, a roll coater, a die coater, or screen printing can be used. The coating thickness can be adjusted by selecting the number of coatings and the paste viscosity, and is usually about 5 to 500 μm. However, the pattern forming method of the present invention is more effective than the conventional photosensitive paste for thick films exceeding 50 μm. Expresses the effect of high sensitivity.

  Further, when the photosensitive paste is applied on the substrate, the surface of the substrate may be treated with a surface treatment liquid in order to improve the adhesion between the substrate and the coating film.

  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% with an organic solvent such as ethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol.

  The surface treatment method can be carried out, for example, by uniformly applying the surface treatment liquid on the substrate with a spinner or the like and then drying it to remove the organic solvent used in the surface treatment liquid. A known method can be used as the method.

For the coating film obtained as described above, (II) is a step of removing the organic solvent remaining in the coating film. Preferably, the coating film on the substrate is heated at a temperature of 70 to 140 ° C. for 5 to 60 minutes. For the heat treatment, a heating device such as a hot plate or a far-infrared oven can be used. In the heat treatment, the temperature condition is preferably 80 to 130 ° C, more preferably 85 to 120 ° C. On the other hand, the treatment time is preferably in the range of 10 to 50 minutes, more preferably in the range of 20 to 40 minutes.
Next, the heat-treated coating film is cooled to room temperature. Such cooling may be allowed to cool. “Room temperature” means about 25 ± 5 ° C.
When such a heat treatment is applied to the coating film, the sensitivity relating to (III) exposure described later can be further improved. Although it is not certain, such a heat treatment can almost remove the organic solvent in the coating film, but still a few percent of the organic solvent tends to remain, and if a small amount of organic solvent remains in the coating film in this way, the coating film It is estimated that the transparency of the material is improved and the sensitivity is improved.

  Next, (III) exposure is performed using an exposure apparatus. For example, a proximity exposure machine or the like can be used as the exposure apparatus.

  In addition, in the case of performing exposure of a large area, after forming a coating film from a photosensitive paste on a substrate as described above, by performing exposure while moving, an exposure machine having a small exposure area can provide a large area. Can be exposed. The exposure is to draw the mask pattern to be created on the photosensitive paste coating film with ionizing radiation. As the ionizing radiation, for example, ultraviolet rays, electron beams, X-rays, visible light, near infrared light, etc. are used. can do.

The amount of irradiation in the exposure can be optimized as appropriate depending on the type of exposure source used or the type of (C) used in the photosensitive paste. In the present invention, a high pressure is used as the exposure source by heat treatment according to (IV) described later. using the wavelength 365nm of light source include mercury lamps, when exposed at room temperature, it is possible to pattern formation in low exposure amount of about exposure ^{100mJ / cm 2 ~300mJ / cm 2} .

Next, (IV) heat treatment after exposure will be described.
The heat treatment after the exposure is performed at a temperature of 80 to 160 ° C. for 3 to 60 minutes. 90-155 degreeC is preferable and the process temperature in this heat processing is further more preferable in it being 100-150 degreeC. On the other hand, the time is preferably in the range of 5 to 50 minutes, and more preferably in the range of 8 to 40 minutes. According to such post-exposure heat treatment, when the coating film obtained from the photosensitive paste is exposed, the development contrast between the unexposed area and the exposed area can be increased, and pattern formation with high sensitivity is possible. And
Further, after the heat treatment, the exposed coating film is cooled to room temperature by cooling or the like.

  Subsequently, (V) development is performed to dissolve unexposed portions and leave exposed portions (photocured portions) to form a pattern. The development is usually performed by an immersion method, a spray method, a brush method, or the like.

  Examples of the developer used for development 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 removability of the portion to be developed and removed is good, and the pattern to be left is less likely to be peeled off or eroded, which is preferable.

  The temperature during development is preferably 15 to 50 ° C. in terms of process control.

After forming the pattern as described above, the partition walls can be formed by firing in a (VI) firing furnace. The firing atmosphere and firing temperature vary depending on the type of photosensitive paste and substrate, but the partition walls are formed on the substrate by firing at 450 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 manufacturing a partition on a glass substrate, it is preferable to perform the heat processing of 450-600 degreeC for 10 to 60 minutes.

  A coat layer may be formed on the surface of the partition wall obtained as described above. 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 point glass particles and a binder resin, and baking it to form on the surface of the partition wall, or after forming the pattern, the coating agent It may be formed on the surface of the partition simultaneously with the formation of the partition by baking after coating.

  Examples of the low melting point glass particles include the same examples as described above.

  Examples of the binder resin include butyral resin, polyvinyl alcohol, acrylic resin, poly α-methylstyrene, and the like.

  As the ceramic coating agent, an aqueous metal salt coating agent, an alkoxy metal salt coating agent, or the like can be used. Specifically, as the aqueous metal salt coating agent, MS-1700, an alkoxy metal salt coating agent is used. As examples, G-301 and G-401 (both manufactured by Nippon Ceramic Co., Ltd.) can be mentioned.

  The firing temperature of the coating layer is usually about 250 to 600 ° C. when a paste agent composed of low melting glass particles and a binder resin is used, and is usually room temperature to 500 ° C. when a ceramic coating agent is used.

By the above patterning method including exposure and development, partition walls with very small dimensional variation before and after firing can be obtained.
The photosensitive paste applied to the present invention has a very low dimensional variation within ± 30%, more preferably within ± 10%, in each of the top width dimension, the bottom width dimension, and the height dimension before and after firing. Since it is a partition and is manufactured by a highly sensitive lithography process, it is possible to manufacture the partition with excellent productivity.

The partition obtained in this way can be suitably used as a partition for a back plate which is a member for plasma display. The manufacturing method of the back plate is achieved by subjecting the substrate on which the partition walls are formed to a known process such as forming a fluorescent layer.
The back plate manufactured in this way is sealed with a front plate for plasma display manufactured by a known method, and discharge gas is sealed in a space formed between the front plate and the back plate. A plasma display panel can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

Production Example 1
<Synthesis of Resin (B-3)>
333 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, after the temperature of the solution in the flask was raised to 100 ° C., 22.0 g (0.10 mol) of dicyclopentanyl methacrylate (FA-513M; manufactured by Hitachi Chemical Co., Ltd.), 70.5 g of benzyl methacrylate (0 .40 mol), 43.0 g (0.5 mol) of methacrylic acid, 3.6 g of azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate were dropped into the flask using a dropping funnel over 2 hours. After completion of the dropwise addition, stirring was further continued at 100 ° C. for 5 hours.
After the stirring was completed, air was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was changed to air. Then, 35.5 g of glycidyl methacrylate [0.25 mol (based on methacrylic acid used in this reaction)] (Corresponding to b24)], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask and the reaction was continued at 110 ° C. for 6 hours. Substitution with ethylene glycol diacetate gave Resin B-3 with a solid content of 50% and an acid value of 80 mgKOH / g.

Here, the acid value is a value measured as an amount (mg) of potassium hydroxide necessary to neutralize 1 g of a polymer having an acid group such as carboxylic acid, and is usually a potassium hydroxide aqueous solution having a known concentration. It is calculated | required by titrating using.
The weight average molecular weight of polystyrene conversion measured by GPC method of the obtained resin B-3 was 9,000.

The measurement of the weight average molecular weight and number average molecular weight of said resin by polystyrene conversion by GPC method was performed on condition of the following.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 ml / min
Test liquid solid concentration: 0.001 to 0.01% by mass
Injection volume: 50 μl
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)
Moreover, the weight average molecular weight was measured under the same conditions for the other resins used in this example.

The raw materials in the photosensitive paste used in the present invention were used in combination with the following.
(A-1) Spherical silica (manufactured by Admatechs; SO-C6)
(A-2) Low melting point lead-free glass particles (manufactured by Yamato Electronics Co., Ltd., YEB2-6701)
(B-1) Ethylene glycol diacetate 50 wt% solution of phenol novolac resin (manufactured by Gunei Chemical Industry Co., Ltd., PSM-4326)
(B-2) Polyacrylic acid (manufactured by Aldrich Mw: 1250) 50% by weight solution of gamma-butyrolactone (B-3) described in Synthesis Example (C-1) 1,3-di (3′-glycidyloxypropyl) -1,1,3,3-tetramethyl-disiloxane (Rodel, SILCOLEASE PC-606PEX)
(I-1) Pentaerythritol tetramethacrylate (D-1) Rhodosyl photoinitiator (Rodel, PI-2074)
(G-1) Sensitizer (manufactured by Kawasaki Chemical Industry Co., Ltd., DBA)
(G-2) 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (G-3) 2,4-diethylthioxanthone (E-1) ethylene glycol diacetate (manufactured by Tokyo Chemical Industry) )
(E-2) 1,2-propanediol dibenzoate (manufactured by Aldrich)
(E-3) Gamma-butyrolactone (H-1) titanium oxide particles (Ishihara Sangyo Co., Ltd., CR-EL)

Example 1
(A-1) 273.2 parts by mass (A-2) 409.7 parts by mass (B-1) 204.9 parts by mass (B-2) 17.1 parts by mass (C-1) 38.4 parts by mass (D-1) 9.8 parts by mass (G-1) 2.1 parts by mass (E-1) 21.3 parts by mass (E-2) 21.3 parts by mass (H-1) 2.1 parts by mass Was put in a polypropylene sealed container and stirred using a stirring defoaming machine (manufactured by Keyence Corporation; HM-500) to prepare a uniform photosensitive paste.

  The prepared photosensitive paste was applied once on a dielectric-coated glass substrate using a 200 μm gap applicator. After coating, the coating film was prepared by drying in an oven at 90 ° C. for 40 minutes.

Next, the dried coating film was exposed with a proximity exposure machine (Dainippon Screen Mfg. Co., Ltd .; MAP-1300) using a 45 μm line, 240 μm pitch mask. The irradiation exposure dose was 200 mJ / cm ² . After the exposure, the substrate was baked at 140 ° C. for 10 minutes, and then developed with a 0.4 mass% sodium hydroxide aqueous solution to obtain a pattern having a pattern upper width of 34 μm, a pattern lower width of 65 μm, and a height of 93 μm. Furthermore, no residue was observed in the unexposed area, and the adhesion to the substrate was good.

Comparative Example 1
(A-1) 273.2 parts by mass (A-2) 409.7 parts by mass (B-1) 204.9 parts by mass (B-2) 17.1 parts by mass (C-1) 38.4 parts by mass (G-2) 9.8 parts by mass (G-3) 2.1 parts by mass (E-1) 21.3 parts by mass (E-2) 21.3 parts by mass (H-1) 2.1 parts by mass Was put in a polypropylene sealed container and stirred using a stirring defoaming machine (manufactured by Keyence Corporation; HM-500) to prepare a uniform photosensitive paste.

  The prepared photosensitive paste was applied once on a dielectric-coated glass substrate using a 200 μm gap applicator. After coating, the coating film was prepared by drying in an oven at 90 ° C. for 40 minutes.

Next, the dried coating film was exposed with a proximity exposure machine (Dainippon Screen Mfg. Co., Ltd .; MAP-1300) using a 45 μm line, 240 μm pitch mask. The irradiation exposure dose was 400 mJ / cm ² . After exposure, development was performed with a 0.4 mass% aqueous sodium hydroxide solution. As a result, the pattern was hardly left due to insufficient exposure.

Comparative Example 2
(A-1) 273.2 parts by mass (A-2) 409.7 parts by mass (B-3) 222.0 parts by mass (I-1) 38.4 parts by mass (D-1) 9.8 parts by mass (G-1) 2.1 parts by mass (E-2) 21.3 parts by mass (E-3) 21.3 parts by mass (H-1) 2.1 parts by mass were placed in a polypropylene sealed container and stirred and removed. A uniform photosensitive paste was prepared by stirring using a foaming machine (manufactured by Keyence Corporation; HM-500).

  The prepared photosensitive paste was applied once on a dielectric-coated glass substrate using a 200 μm gap applicator. After coating, the coating film was prepared by drying in an oven at 90 ° C. for 40 minutes.

Next, the dried coating film was exposed with a proximity exposure machine (Dainippon Screen Mfg. Co., Ltd .; MAP-1300) using a 45 μm line, 240 μm pitch mask. The irradiation exposure dose was 400 mJ / cm ² . After exposure, development was performed with a 0.4 mass% aqueous sodium hydroxide solution. As a result, the pattern was hardly left due to insufficient exposure.

Claims (12)

Each step;
A photosensitive paste containing (I) (A) inorganic particles, (B) an alkali-soluble resin, (C) a crosslinking agent, (D) an acid generator and (E) an organic solvent is applied onto the substrate, A step of obtaining a coating film,
(II) a step of removing the organic solvent remaining in the coating film obtained by the step (I) (III) a step of exposing the coating film on the substrate obtained by the step (II),
(IV) A step of heating the coating film exposed in step (III) at 80 ° C. to 160 ° C. for 3 minutes to 60 minutes and then cooling to room temperature,
(V) A step of developing the coating film obtained in step (IV) to form a pattern on the substrate,
(VI) A pattern forming method comprising a step of firing the pattern obtained in the step (V) at a temperature of 450 ° C. to 600 ° C. together with the substrate. After the step (II) heats the coating film on the substrate obtained in the step (I) at 70 ° C. to 140 ° C. for 5 minutes to 60 minutes, the coating film remains on the coating film by cooling to room temperature. The pattern forming method according to claim 1, which is a step of removing the organic solvent. 3. The pattern forming method according to claim 1, wherein (E) comprises an organic solvent (E-a) having a boiling point at 1 atm of 100 ° C. or more and less than 195 ° C. as an essential component. 4. The pattern forming method according to claim 3, wherein when the total amount of (E) is 100 mass%, the organic solvent (E-a) is 70 mass% or more. The pattern forming method according to claim 3, wherein the organic solvent (Ea) is ethylene glycol diacetate. All the organic solvents which comprise the said (E) are organic solvents whose refractive index in 25 degreeC is 1.40-1.80. The pattern formation method in any one of Claims 1-5. The (B) alkali-soluble resin is a novolac resin and / or a novolac resin derivative, and the (C) crosslinking agent is an epoxy-containing silicon compound represented by the following formula (3): The pattern formation method as described.

(In the formula, Q ₂ and Q ₃ are each independently a group represented by the formula (4), and Q ₁ represents a divalent group represented by the formula (5a) or the formula (5b).)

(In the formula, T ₁ represents an alkylene group having 1 to 6 carbon atoms, an alkyleneoxyalkylene group having 1 to 6 carbon atoms, or a phenylene group. M is 0 or 1.)

(Wherein T _{2 to} T ₇ represent a methyl group or a phenyl group. T ₈ is selected from the group consisting of an oxygen atom, a methylene group, an ethenylene group, an ethynylene group, a phenylene group, a naphthalenediyl group, and a biphenyldiyl group. .) The pattern forming method according to any one of claims 1 to 7, wherein (A) is an inorganic particle containing low melting point glass particles having a softening point of 400C to 600C. The content ratios of (A) to (E) in the photosensitive paste are (A) 20 to 95% by mass, (B) 2 to 30% by mass, (C) 1 to 30% by mass, and (D), respectively. It is 0.01-20 mass% and (E) 1-40 mass%, The pattern formation method in any one of Claims 1-8. The partition for plasma display panels manufactured using the pattern formation method in any one of Claims 1-9. The member for plasma displays provided with the partition for plasma display panels of Claim 10. A plasma display panel comprising the member for plasma display according to claim 11.