JP5178178B2 - Photosensitive resin composition and method for producing fired product pattern obtained using the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition used for forming various patterns constituting a plasma display panel (hereinafter abbreviated as PDP) and a method for producing a fired product pattern using the same.

  The PDP is a flat display that displays images and other information using light emission by plasma discharge. The principle of image display by this PDP, particularly color display, is that the space between the front glass substrate and the back glass substrate is separated by ribs (partition walls) to form a plurality of cell spaces (discharge spaces), and the front glass substrate A plasma discharge is generated in the cell space by applying an AC voltage between the electrodes wired in a matrix on the back glass substrate. That is, a gas that is a discharge medium such as He and Xe is sealed in the plurality of cell spaces, and phosphors that emit three primary colors are applied to the inner surface of the rear glass substrate that forms the cell spaces. ing. Plasma discharge is generated in each cell space by applying a voltage between the electrodes arranged in a matrix. Color display is performed by exciting the phosphors emitting the three primary colors with ultraviolet rays generated by this discharge.

  In recent years, in a PDP having such a structure, a high density and high definition of a display image are required, and a high density and high definition of various patterns constituting a PDP display panel are required. As means for satisfying such requirements, patterning by exposure and development using a photolithography method in which an ultraviolet curable resin composition is coated on a front panel or a back panel has been used. In this method, alkali development is generally used, and therefore an organic polymer compound containing a carboxyl group is used for the photosensitive paste.

  However, in order to prepare a photosensitive resin composition, it is obtained by adding a powder containing a polyvalent metal such as glass powder or ceramic powder or an oxide thereof to an organic polymer compound containing a carboxyl group as described above. The resulting photosensitive resin composition is likely to be thickened or gelled. The reason is considered to be that the polyvalent ions eluted from the powder and the carboxyl group of the organic polymer compound are ion-crosslinked. When gelation or thickening of such a photosensitive resin composition occurs, for example, when the photosensitive resin composition is applied to a substrate by screen printing, unevenness cannot be achieved and uniform application is not possible. There may not be.

As a method for preventing gelation and thickening of such a photosensitive resin composition, it has been conventionally proposed to contain lactic acid, malic acid, citric acid, oxalic acid and the like as a storage stabilizer (Patent Document 1). reference). However, this method has storage stability that suppresses gelation and thickening, but the resolution of the pattern using the photosensitive resin composition is lowered, and there is a limit to the formation of a fine pattern.
JP-A-9-222723

  The present invention has been made in order to solve such problems of the prior art, and its main purpose is excellent storage stability and high development without reducing developability even when forming a fine pattern. An object of the present invention is to provide a photosensitive resin composition capable of forming a fine pattern, and to provide a method for forming a fine pattern using the same.

In order to achieve the above object, the photosensitive resin composition of the present invention comprises (A) inorganic fine particles comprising at least one kind of glass fine particles and conductive powder , (B) carboxyl group-containing resin, and (C) photopolymerizable. monomer is characterized by containing at least one storage stabilizer, the (D) photopolymerization initiator, (E), thioglycolic acid, thio diglycolic acid.

  According to the present invention, it is possible to obtain a photosensitive resin composition that is excellent in storage stability and capable of forming a high-definition pattern without deteriorating developability when forming a fine pattern. Further, according to the production method of the present invention, by using such a photosensitive resin composition, a high-definition fired product pattern can be formed in a PDP panel.

  The best embodiment of the present invention will be described in detail below.

The photosensitive resin composition of the present invention comprises (A) inorganic fine particles, (B) carboxyl group-containing resin, (C) photopolymerizable monomer, (D) photopolymerization initiator, and (E) glycolic acid, thioglycolic acid And at least one storage stabilizer of thiodiglycolic acid . The present invention relates to a method for manufacturing a flexible printed wiring board or a thin printed wiring board that requires flexibility, for example.

  Hereinafter, each component of the photosensitive resin composition will be described.

The (A) inorganic fine particles may be used conventionally known inorganic fine particles may be used particularly preferably at least one of the glass fine particles及 beauty conductive powder.

  The glass fine particles mainly contain glass having a glass transition point (Tg) of 300 to 500 ° C. and a glass softening point (Ts) of 400 to 600 ° C., such as lead oxide, bismuth oxide, zinc oxide or lithium oxide. Glass to be used is preferably used. From the viewpoint of resolution, it is preferable to use glass powder having an average particle size of 10 μm or less, particularly 5 μm or less.

  The black pigment is used when black is required for the fired product pattern, for example, black made of one or more metal oxides of Co, Ni, Cu, Fe, Mn, Al, Ru, La, and Sr. Pigments can be used. In particular, it is preferable to use cobalt oxide fine particles, in particular, tribasic cobalt tetroxide fine particles, because the formed black film becomes dense and even a thin film can exhibit sufficient blackness. It is desirable to use fine particles having an average particle diameter of 2 μm or less, preferably 0.1 to 1 μm. This is because if the average particle size is 2 μm or less, a dense fired film can be formed without impairing adhesion and the like even with a small amount of addition, and sufficient blackness can be obtained. On the other hand, when the average particle diameter of the black pigment is larger than 2 μm, the denseness of the fired film is deteriorated, and the blackness is easily lowered. On the other hand, if the thickness is smaller than 0.1 μm, the hiding power is lowered and a transparency may appear, which is not preferable.

  The black pigment is preferably used as a slurry dispersed in a solvent. This slurry can be prepared by dispersing a black pigment in a solvent according to a conventionally known method. For example, a solvent, a dispersant, and a black pigment are mixed and prepared using a mixer such as a ball mill. The pigment concentration in the slurry can be arbitrarily set, but is preferably 50 to 80% in consideration of workability and the like.

  Examples of the conductive powder include silver (Ag), gold (Au), nickel (Ni), copper (Cu), aluminum (Al), tin (Sn), platinum (Pt), and ruthenium (Ru). In addition to simple substances and alloys thereof, tin oxide (SnO2), indium oxide (In203), ITO (Indium Tin Oxide), ruthenium oxide (RuO2), and the like can be used. These can be used alone or as a mixed powder of two or more.

  Various shapes such as a spherical shape, a flake shape, and a dentrite shape can be used for the conductive powder, but it is preferable to use a spherical shape in consideration of optical characteristics and dispersibility. The average particle diameter is preferably 10 μm or less, preferably 5 μm or less from the viewpoint of the line shape.

  These conductive powders are preferably blended at a ratio of 50 to 2,000 parts by mass when the total amount of the resin composition components is 100 parts by mass. When the blending amount of the conductive powder is less than 50 parts by mass, the conductor circuit line width shrinkage or disconnection is likely to occur. On the other hand, when the blending amount exceeds 2,000 parts by mass, light transmission is impaired, It becomes difficult to obtain sufficient photocurability. Furthermore, in order to improve the strength of the film after firing and the adhesion to the substrate, the glass fine particles can be added at a ratio of 1 to 30 parts by mass per 100 parts by mass of the metal powder.

  As other inorganic fine particles, silk powder, particularly synthetic amorphous silica fine powder, can be used as long as it does not adversely affect the fired product pattern.

  Specific examples of the synthetic amorphous silica fine powder include AEROSIL (registered trademark) 50, 130, 200, 200V, 200CF, 200FAD, 300, 300CF, 380, OX50, TT600, MOX80, MOX170, manufactured by Nippon Aerosil Co., Ltd. COK84, Nipsil (registered trademark) AQ, AQ-S, VN3, LP, L300, N-300A, ER-R, ER, RS-150, ES, NS, NS-T, NS -P, NS-KR, NS-K, NA, KQ, KM, DS and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, those having a primary particle diameter of 5 to 50 μm and a specific surface area of 50 to 500 m 2 / g are preferable.

  Next, the carboxyl group-containing resin (B) may be a photosensitive resin or a non-photosensitive resin, and these may be used alone or in combination. In any case, it is preferable to add these at a ratio of 10 to 80% by mass based on the total amount of the composition. When the blending amount of these resins is too smaller than the above range, the distribution of the resin in the film to be formed tends to be uneven.

Among the carboxyl group-containing resins (B), as the non-photosensitive resin,
(1) a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid and a compound having an unsaturated double bond,
(2) An epoxy group of a copolymer of an epoxy group, a compound having an unsaturated double bond and a compound having an unsaturated double bond has one carboxyl group in one molecule, and has an ethylenically unsaturated bond. Obtained by reacting a polybasic acid anhydride with the resulting secondary hydroxyl group, and (3) reacting the polybasic acid anhydride with a hydroxyl group-containing polymer. And carboxyl group-containing resins.

Of the carboxyl group-containing photosensitive resin (B), as the photosensitive resin,
(1) A carboxyl group-containing photosensitive resin obtained by partially adding an ethylenically unsaturated group as a pendant to a carboxyl group of a copolymer of a compound having an unsaturated carboxylic acid and an unsaturated double bond,
(2) An epoxy group of a copolymer of a compound having an epoxy group and an unsaturated double bond and a compound having an unsaturated double bond is reacted with an unsaturated carboxylic acid, and the resulting secondary hydroxyl group is converted to a polybasic acid. A carboxyl group-containing photosensitive resin obtained by reacting an anhydride,
(3) A carboxyl group-containing photosensitive resin obtained by reacting a copolymer of an acid anhydride having an unsaturated double bond and a compound having an unsaturated double bond with a compound having a hydroxyl group and an unsaturated double bond ,
(4) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the resulting secondary hydroxyl group with a polybasic acid anhydride, and (5) a hydroxyl group-containing polymer. Examples thereof include a carboxyl group-containing photosensitive resin obtained by further reacting a compound having an epoxy group and an unsaturated double bond with a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride.

  The carboxyl group-containing resin (B) has a weight average molecular weight of 1,000 to 100,000, preferably 5,000 to 70,000, and an acid value of 20 to 250 mgKOH / g, preferably 50 to 150 mgKOH / g. It is. When the molecular weight of the resin is lower than 1,000, the adhesion of the film during development is adversely affected. On the other hand, when the molecular weight is higher than 100,000, poor development is likely to occur, which is not preferable. Further, when the acid value is lower than 20 mgKOH / g, the solubility in an alkaline aqueous solution is insufficient, and development failure tends to occur. ) Is not preferable. Further, in the case of a photosensitive resin among the carboxyl group-containing resins (B), those having a double bond equivalent of 350 to 2,000, preferably 400 to 1,500 can be suitably used. If the double bond equivalent of the photosensitive resin is less than 350, residues are likely to remain during baking. If it is greater than 2,000, the work margin during development is narrow, and a high exposure amount is required during photocuring. It is not preferable.

  The photopolymerizable monomer (C) is used for promoting photocurability. Specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, and polyethylene. Glycol diacrylate, polyurethane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate and methacrylates corresponding to the acrylate; Examples include mono-, di-, tri- or higher polyesters of polybasic acids such as phthalic acid, adipic acid, maleic acid, itaconic acid, succinic acid, trimellitic acid, and terephthalic acid, and hydroxyalkyl acrylate or hydroxyalkyl methacrylate. . However, it is not limited to a specific thing, These can be used individually or in combination of 2 or more types. Among the photopolymerizable monomers (C), polyfunctional monomers having two or more acryloyl groups or methacryloyl groups in one molecule are preferable.

  The blending amount of the photopolymerizable monomer (C) is preferably 20 to 100 parts by mass per 100 parts by mass of the carboxyl group-containing resin (B). When the blending amount of the photopolymerizable monomer (C) is less than the above range, it becomes difficult to obtain sufficient photocurability of the composition. As a result, photocuring of the surface portion is accelerated, and curing unevenness is likely to occur.

  Specific examples of the photopolymerization initiator (D) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-phenylacetophenone, 2,2 Acetophonones such as diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2 Aminoacetophenones such as dimethylamino-1- (4-morpholinophenyl) -butanone-1; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 4-dimethylthioxanthone, 2,4-diethi Thioxanthones such as thioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenones such as benzophenone; or Xanthones; (2,6-dimethoxybenzoyl) -2 , 4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenyl Examples include phosphine oxides such as phosphinate; various peroxides. These known and commonly used photopolymerization initiators can be used alone or in combination of two or more.

  In addition, the photopolymerization initiator (D) includes N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. It can be used in combination with one or more of photosensitizers such as secondary amines.

  The blending ratio of the photopolymerization initiator (D) and the photosensitizer is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass per 100 parts by mass of the carboxyl group-containing resin (B). And

  In the present invention, the storage stabilizer (E) is contained in order to prevent gelation and thickening. Specific examples of the storage stabilizer (E) include glycolic acid, glycolic acid ethyl ether, phenoxyethyl glycolate, diglycolic acid, phenyldiglycolic acid, methyldiglycolic acid, 2-0-phosphoglycolic acid, thioglycol Acid, thiodiglycolic acid, dithioglycolic acid, 2- (acetylthio) acetic acid, S- (thiobenzoyl) thioglycolic acid, S- (4-pyridylthio) thioglycolic acid, (2-pyridylthio) acetic acid, chlorotolylthioglycol Acid, 2,5-dichlorophenylthioglycolic acid, S-benzylthioglycolic acid, trithiocarbodiglycolic acid, S-methylthioglycolic acid, S- (2-naphthyl) thioglycolic acid, S-nitrosothioglycolic acid, S -Benzoylthioglycolic acid, S- (benzoxazol-2-ylthio) thioglycolic acid, S -(4-Methylphenylthio) thioglycolic acid, (3-methoxyphenylthio) acetic acid, etc. are mentioned, These can be used individually or in combination of 2 or more types.

The amount of the storage stabilizer (E), the weight per 100 parts by weight of the glass fine particles of the inorganic fine particles (A), 0.1 to 10 parts by weight, more preferably 0.5 to 5.0 parts by weight It is. When the amount of the storage stabilizer (E) is less than the above range, it is difficult to obtain sufficient storage stability of the composition, and conversely, when the amount exceeds the above range, the film resistance at the time of pattern formation The characteristics are deteriorated, and pattern defects are likely to occur.

  The photosensitive resin composition of the present invention may be blended with additives such as silicone-based and acrylic-based defoaming / leveling agents and silane coupling agents for improving film adhesion, if necessary. Can do. Further, fine particles such as metal oxide, silicon oxide, boron oxide and the like as a binding component with a substrate used at the time of firing can be added as necessary.

  The photosensitive resin composition of the present invention is prepared by mixing and dispersing the above-described various components so as to have a predetermined composition using a three-roll mill or a kneader.

  The photosensitive resin composition of the present invention as described above may be laminated on a substrate when it is previously formed into a film, but in the case of a paste, a screen printing method, a bar coater, A substrate such as a blade coater is applied to a substrate, for example, a glass substrate serving as a front substrate of a PDP, and then in order to obtain dryness to touch, in a hot air circulation drying furnace or a far infrared drying furnace, for example, 60 to 120 The organic solvent is evaporated by drying at about 5 to 40 minutes to obtain a tack-free coating film. Thereafter, selective exposure, development and firing are performed to form a predetermined fired product pattern.

  Here, the selective exposure can be contact exposure or non-contact exposure using a negative mask having a predetermined exposure pattern. As the exposure light source, a halogen lamp, a high-pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, an electrodeless lamp, or the like is used. The exposure amount is preferably about 50 to 1,000 mJ / cm @ 2.

  For the development, a spray method, a dipping method or the like is used. Developers include aqueous alkali metal solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium silicate, and aqueous amine solutions such as monoethanolamine, diethanolamine, and triethanolamine, particularly a concentration of 1.5% by mass or less. The dilute alkaline aqueous solution is preferably used, but the carboxyl group of the carboxyl group-containing resin in the composition may be saponified and the uncured part (unexposed part) may be removed, and is limited to the developer as described above. Is not to be done.

  Firing can be carried out under conditions of 400 to 600 ° C. in air or in a nitrogen atmosphere to form a desired fired product pattern. In addition, it is preferable to set the temperature increase rate at this time to 20 degrees C / min or less.

  Moreover, the said inorganic fine particle (A) component can be suitably selected according to the kind of desired baked material pattern. For example, in the case of forming an electrode pattern, a conductive powder is used, but it is preferable to use an appropriate amount of glass fine particles in combination in order to improve the firing property. In particular, when forming a black electrode pattern, a black pigment is also used. In the case of a black matrix pattern, glass fine particles and a black pigment are used, and glass fine particles are used for forming the partition pattern.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples. “Parts” and “%” are based on mass unless otherwise specified.

[PDP display panel electrode wiring paste]
(Synthesis example of organic binder A)
In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst were heated to 80 ° C. in a nitrogen atmosphere, and methacrylic acid and A monomer in which methyl methacrylate is mixed at a molar ratio of methacrylic acid: 0.4 mol and methyl methacrylate: 0.6 mol is added dropwise over 2 hours, and after stirring for another hour, the temperature is raised to 115 ° C. to deactivate the monomer, A resin solution was obtained.

  Next, after cooling this resin solution, tetrabutylammonium bromide was used as a catalyst, 95 ° C. to 105 ° C., 30 hours, butyl glycidyl ether: 0.4 mol, equivalent amount of carboxyl group of the obtained resin And the reaction was cooled.

  Further, 0.26 mol of tetrahydrophthalic anhydride was added to the OH group of the obtained resin under conditions of 95 to 105 ° C. for 8 hours, cooled and taken out, and then an organic binder having a solid content of 55% (hereinafter referred to as organic). Binder A) was obtained.

The organic binder A obtained as described above was blended at the composition ratio shown in Table 1, stirred with a stirrer, and then kneaded with a three-roll mill to obtain a photosensitive resin composition.
As the glass frit, glass of Bi2O3 49%, B2O3 14%, ZnO 14%, SiO2 6%, BaO 17% was crushed to have a glass transition point of 457 ° C. and an average particle size of 1.6 μm. used. The particle size of the glass frit was measured with a laser diffraction / scattering particle size distribution analyzer: LMS-30 (manufactured by Seishin Enterprise Co., Ltd.). Further, the average particle size as silver powder (measured by a laser diffraction / scattering particle size distribution analyzer): 2.2 μm, specific surface area (measured by the BET single point method): 0.50 m 2 / g, tap density (measured by a tap density meter): 4.4 was used.

The components shown in Table 1 below were blended, stirred with a stirrer, and then slaughtered with a three roll mill to obtain a photosensitive resin composition.

About the obtained photosensitive resin composition (paste), developability, storage stability, etc. were evaluated. These evaluation results are shown in Table 2. The evaluation method is as follows.
(Evaluation Substrate) The evaluation pastes of Examples and Comparative Examples were applied on the entire surface of a glass substrate with an ITO film using a 200 mesh polyester screen. Next, the substrate was dried at 90 ° C. for 20 minutes in a hot air circulation drying oven to form a film having good touch drying properties. Then, using an ultra-high pressure mercury lamp (made by Ushio Corporation, short arc lamp 5KW) as the light source, using a striped negative mask having a line width of 10 to 100 μm and a space width of 100 μm, the integrated light quantity on the composition becomes 300 mJ / cm 2. Were exposed as follows. Further, a Kodak No. 2 step tablet was used and exposed in the same manner. After the exposure, development using an aqueous solution of 0.4 wt% Na2CO3 at a liquid temperature of 30 ° C. was performed for 30 seconds or 60 seconds and washed with water.

O Coating thickness after drying (μm): After drying, the coating thickness was measured with a surface roughness meter manufactured by Kosaka Laboratory.
○ Sensitivity: Kodak No. 2 step tablets were used, and the number of stages remaining after development was evaluated.
○ Film thickness after development (μm): The height of the mask width 100 μm line was measured with a surface roughness meter manufactured by Kosaka Laboratory.
○ Line width after development (μm): Mask width 100 μm Line width was measured using an optical microscope. Note that NG means that measurement is impossible because no line width remains.
Undercut (μm): After development, the undercut width on one side of the mask width 100 μm line from the back surface was measured with an optical microscope. Note that NG means that measurement is impossible because no line remains after development.
○ Complete residual pattern (μm): line width L / space width S = 40/80, 60/80, 80/80, 100/300, 200/300, 300/300 length 2 cm, 8 lines each The minimum line width (μm) that can be formed after development in the dense line patterns arranged in parallel was evaluated as a complete residual pattern. In addition, NG means that measurement is impossible because no line remains.

(Storage stability)
○ Printability after one month at 25 ° C .: The compositions of Examples and Comparative Examples were stored at 25 ° C. for one month, and examined whether there was any problem with printability in terms of unevenness, and storage stability was evaluated. .

  As is clear from the results shown in Table 2, with respect to the film thickness after development, when the development time is 30 seconds, the film thickness is almost the same in both the example and the comparative example, whereas the development time In the case of 60 seconds, it is 11.0 to 11.3 μm in the examples, while in Comparative Examples 2 to 5, it is NG, that is, the measurement cannot be performed because no line remains after development. Obtained.

  As for the line width after development, similarly, when the development time is 30 seconds, the line width of almost the same degree is obtained in both the example and the comparative example, whereas in the case where the development time is 60 seconds, the example In Comparative Examples 2 to 5, a result of NG was obtained.

  Regarding the undercut, when the development time is 30 seconds, each of Examples 1 and 2 is 9 μm, while in Comparative Examples 2 to 5, they are 10.5, 11, 14.5, and 9 μm, respectively. Except for the comparative example 5, the undercut is smaller in the case of the example of the present invention. When the developing time was 60 seconds, the results were 14 to 16 μm in the examples, whereas NG was obtained in Comparative Examples 2 to 5.

  Regarding the completely remaining pattern, when the development time was 30 seconds, a thin line pattern of 40 μm was formed in each of Examples 1 and 2, whereas in Comparative Examples 3 and 5, the same was 40 μm. 2 was 60 μm, and Comparative Example 4 was 100 μm. Further, when the development time is 60 seconds, in the example, it is 80 to 100 μm, whereas in Comparative Examples 2 and 3, only thick line patterns of 200 and 300 are formed, respectively. 5, the result was that NG, that is, all the wiring patterns including the thickest wiring pattern 300/300 disappeared.

  In Comparative Example 1, each of the evaluation items other than the storage stability is equal to or better than the examples of the present invention, but there is a problem in terms of storage stability, and it is practically used. I don't get it. That is, regarding the storage stability, the printability of the photosensitive resin compositions of Examples and Comparative Examples which were stored for 1 month under the condition of 25 ° C. was examined, but Comparative Examples 1 and 2 had problems. On the other hand, the examples were good without degrading the resolution at the time of preparing the photosensitive resin composition.

  When the above results are put together, it can be seen that the photosensitive resin compositions of Examples 1 and 2 of the present invention have sufficient storage stability and can form a high-definition development pattern.

  As described above, the photosensitive resin composition according to the present invention can create a high-definition development pattern and a high-definition fired product pattern based thereon, and is excellent in storage stability.

[Black matrix pattern forming paste]
(Synthesis example of organic binder B)
A flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser is charged with methyl methacrylate and methacrylic acid in a molar ratio of 0.87: 0.13, diethylene glycol monomethyl ether acetate as a solvent, and azobisisobutyrate as a catalyst. Ronitrile was added and stirred at 80 ° C. for 2 to 6 hours under a nitrogen atmosphere to obtain an organic binder B.
This organic binder B had a weight average molecular weight of about 40,000, an acid value of 103 mgKOH / g, and a solid content of 29%. In addition, the measurement of the weight average molecular weight of the obtained organic binder B (copolymerization resin) measured Shimadzu pump LC-6AD and Showa Denko column Shodex (registered trademark) KF-804, KF-803, KF-802. The measurement was performed by high performance liquid chromatography connected to a triplet.

The organic binder B thus obtained was blended at the composition ratio shown in Table 3, stirred with a stirrer, and then kneaded with a three-roll mill to obtain a photosensitive resin composition.
As the glass frit, glass of Bi2O3: 49%, B2O3: 14%, ZnO: 14%, SiO2: 6%, BaO: 17% was crushed, glass transition point: 457 ° C, average particle diameter: 1. What was 6 micrometers was used. The particle size of the glass frit was measured with a laser diffraction / scattering particle size distribution analyzer: LMS-30 (manufactured by Seishin Enterprise Co., Ltd.). The tricobalt tetroxide powder used had an average particle size (measured by a laser diffraction / scattering particle size distribution analyzer): 0.45 μm and a specific surface area (measured by the BET single point method): 6.0 m 2 / g.

About the obtained photosensitive resin composition (paste), storage stability, developability, pattern formability, etc. were evaluated. These evaluation results are shown in Table 4. The evaluation method is as follows.
(Evaluation Substrate) The evaluation pastes of Examples and Comparative Examples were applied on the entire surface of a glass substrate using a 300 mesh polyester screen. Next, the substrate was dried at 100 ° C. for 15 minutes in an IR drying oven to form a film having good touch-drying properties. Then, using a super high pressure mercury lamp (USHIO, short arc lamp 5KW) as a light source, using a striped negative mask having a line width of 10 to 100 μm and a space width of 100 μm, the integrated light amount on the composition becomes 600 mJ / cm 2. Were exposed as follows. Further, a Kodak No. 2 step tablet was used and exposed in the same manner. After the exposure, development using an aqueous solution of 0.4 wt% Na 2 CO 3 at a liquid temperature of 30 ° C. was performed for 20 seconds, 40 seconds, and 60 seconds, washed with water, and dried, and each was used as an evaluation substrate.

(Storage stability)
The viscosity of each photosensitive resin composition obtained was measured with a TV-type viscometer manufactured by Tokimec Co., Ltd., then stored at 25 ° C. for 18 days, and then the viscosity was measured again with the same viscometer. From the measured viscosity value, the viscosity increase rate of the clay by storage over time was calculated, and the storage stability was evaluated.

(Pattern formability)
Line width L / space width = 40/80, 60/80, 80/80, 100/300, 200/300, 300/300 length 2 cm, each dense line in which 8 lines are arranged in parallel The pattern was observed with an optical microscope, and the shape of the pattern (such as wobbling of the line) and the adhesion with the substrate (such as lifting and flying) were evaluated.

○ Sensitivity: Kodak No. 2 step tablets were used, and the number of stages remaining after development was evaluated.
○ Film thickness after development (μm): The height of the mask width 100 μm line was measured with a surface roughness meter manufactured by Kosaka Laboratory.
○ Line width after development (μm): Mask width 100 μm Line width was measured using an optical microscope.
○ Complete residual pattern (μm): line width L / space width S = 40/80, 60/80, 80/80, 100/300, 200/300, 300/300 length 2 cm, 8 lines each The minimum line width (μm) that can be formed after development in the dense line patterns arranged in parallel was evaluated as a complete residual pattern.

  As is clear from the results shown in Table 4, regarding the storage stability of the photosensitive resin composition, the photosensitive resin compositions of Examples 3 and 4 and Comparative Example 8 have almost no change in viscosity and suppress increase in viscosity. In contrast, the photosensitive resin compositions of Comparative Examples 6 and 7 had a large viscosity change, and the result was that the viscosity increased.

  In addition, with respect to pattern formability, in Examples 3 and 4 and Comparative Examples 6 and 7, a good pattern was obtained at any of development times of 20 seconds, 40 seconds, and 60 seconds, whereas in Comparative Example 8, Although a good pattern was obtained at the development time of 20 seconds, the formation pattern was lifted from the substrate at 40 seconds, and irregular jumps of the formation pattern were observed at 60 seconds.

  Further, with respect to the completely remaining pattern, in Examples 3 and 4, and Comparative Examples 6 and 7, a 10 μm fine line pattern was formed at both development times of 20 seconds and 40 seconds, whereas in Comparative Example 8, development was performed. The time was 20 μm at 20 seconds and 30 μm at 40 seconds. When the development time was 60 seconds, a thin line pattern of 20 μm was formed in Examples 3 and 4 and Comparative Examples 6 and 7, whereas a result of 30 μm was obtained in Comparative Example 8.

  As described above, Comparative Examples 6 and 7 were almost the same as the Examples with respect to patterning properties such as pattern formability and completely remaining pattern, but there was a problem in terms of storage stability, and they could be put to practical use. Absent. On the other hand, Comparative Example 8 was almost the same as the Example with respect to storage stability, but a result was obtained that there was a problem in patterning properties such as pattern forming property and complete residual pattern.

  When the above results are put together, it can be seen that the photosensitive resin compositions of Examples 3 and 4 have sufficient storage stability and can form a high-definition development pattern.

  As described above, the photosensitive resin composition according to the present invention can create a high-definition development pattern and a high-definition fired product pattern based thereon, and is excellent in storage stability.

  The present invention is not limited to the above embodiments or examples, and various modifications are possible. For example, in the above-described embodiment, the present invention is applied to the electrode wiring for the PDP display panel and the black matrix pattern formation. However, the present invention is not limited to this, and the barrier ribs and the dielectric are formed using such a photosensitive paste. It is also possible to form a fired product pattern such as.

Claims (3)

(A) Inorganic fine particles comprising at least one of glass fine particles and conductive powder , (B) carboxyl group-containing resin, (C) photopolymerizable monomer, (D) photopolymerization initiator, (E) glycolic acid, thioglycol at least one storage stabilizer, a photosensitive resin composition characterized by containing acids and thio diglycolic acid. The storage stabilizer (E) is the weight per 100 parts by weight of the glass fine particles of the inorganic fine particles (A), the photosensitive resin composition according to claim 1, characterized in that 0.1 to 10 parts by weight object. The manufacturing method of the baked product pattern obtained by apply | coating the coating film which consists of the photosensitive resin composition of the said Claim 1 or 2 on a board | substrate, exposing and developing this, and baking.