JP2009073873A - Curable resin composition for mold, method for manufacturing mold, method for manufacturing structure, and method for manufacturing display member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming technology for forming a pattern suitable for a flat display such as a plasma display panel, a field emission display and a fluorescent display tube with high accuracy at a low cost. <P>SOLUTION: The technology can be achieved by a curable resin composition for a mold, the composition containing at least (A) a curable compound, (B) a urethane compound, (C) a polymerization initiator and (D) a surfactant. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable resin composition for a mold, particularly a curable resin composition for a mold suitable for manufacturing a patterned structure of a flat display such as a plasma display panel, a field emission display, and a fluorescent display tube. The present invention relates to a method for producing a mold using the same, a method for producing a structure, and a method for producing a display member.

  In recent years, flat displays such as plasma display panels, field emission displays, fluorescent display tubes, liquid crystal display devices, electroluminescence displays, and light emitting diodes have been rapidly developed. Among these, the plasma display generates a plasma discharge between the anode electrode and the cathode electrode facing each other in the discharge space provided between the front glass substrate and the rear glass substrate, and the gas sealed in the discharge space. Display is performed by irradiating the phosphor provided in the discharge space with the ultraviolet rays generated from the discharge. Gas discharge type displays such as plasma displays and fluorescent display tubes require partition walls for partitioning the discharge space. A field emission display such as a field emission display requires a partition for isolating the gate electrode from the cathode. In the formation of partition walls for these plasma displays and field emission displays, in general, inorganic materials such as glass powder are baked after being patterned, so that inorganic materials such as glass powder can be freely adjusted with high precision and high aspect ratio. In addition, materials and processing methods capable of pattern processing are required. In particular, plasma display partition walls have conventionally been in the form of stripes, but in order to improve luminous efficiency, the conventional stripe-shaped partition walls have been changed to those having a complicated shape such as a lattice-shaped partition wall in which auxiliary partition walls are provided in the vertical direction. . These shapes are difficult to produce by applying a conventional striped manufacturing method.

  On the other hand, there is an imprint method as a method for freely forming a high precision and high aspect ratio pattern. As the imprint method, an optical imprint method and a thermal imprint method are often used. In order to obtain a pattern with high accuracy and a high aspect ratio, the optical imprint method is particularly preferable. In the imprint method, a mold having a desired pattern shape and concavity and convexity is produced, a molding material is filled in the concave portion of the mold, and when using the photoimprint method, it is cured by light irradiation, followed by The desired pattern is obtained by removing the mold.

There is a method of applying this imprint method to the formation of stripe-shaped barrier ribs (Patent Documents 1 to 4). According to this method, first, a mold having an irregular shape opposite to the partition wall is manufactured. Next, the concave portion of the mold is filled with glass paste, the concave portion is pressure-bonded to the substrate, and in the case of the photoimprint method, photocuring is performed, the mold is peeled from the substrate, and the glass paste is transferred to the substrate. To form a barrier rib pattern. Or after apply | coating glass paste to a board | substrate and crimping | bonding a shaping | molding die to glass paste, in the case of the photoimprint method, photocuring is performed and the said shaping | molding die is peeled from a board | substrate and a partition pattern is formed. Thereafter, the barrier rib pattern is baked to remove organic components to obtain a desired barrier rib. However, when this method is applied to a grid-shaped partition wall, there is a problem that the mold is deformed or cracks or breaks occur when the mold is peeled off from the mother mold during the manufacture of the mold. In addition, after filling the glass paste and press-bonding to the substrate, when the mold was peeled from the substrate, the glass paste adhered to the mold, or defects such as cracks, disconnection, and uneven height were likely to occur in the partition pattern. . As a result, it has been difficult to form a complicatedly shaped structure such as a lattice-shaped partition wall at low cost by the conventional method.
Japanese Patent No. 3589500 (Claim 1) Japanese Patent No. 3591910 (Claim 1) JP-A-2001-191345 (Claim 10) Special table 2007-503338 (Claim 19)

  The present invention pays attention to the problems of the prior art described above, and provides a cured resin for a mold that can freely form a structure having a complicated shape such as a lattice-shaped partition wall at a low cost, and a mold, a structure, and a display member. An object is to provide a manufacturing method.

  In order to solve the above problems, the present invention has the following configuration. That is, the said subject is achieved by the curable resin composition for molds containing at least (A) curable compound, (B) urethane compound, (C) polymerization initiator, and (D) surfactant. Is done.

  ADVANTAGE OF THE INVENTION According to this invention, the pattern formation technique which can form patterns, such as a partition of a flat display, such as a plasma display, a field emission display, and a fluorescent display tube, accurately at low cost can be provided.

  As a result of intensive studies on the formation of a high-definition and high-aspect-ratio pattern, the inventors have found that this can be achieved by a curable resin composition for a mold having a composition as described below.

  That is, the curable resin composition for a mold according to the present invention needs to contain (B) a urethane compound. By containing the urethane compound, flexibility and toughness can be imparted to the formed mold, and defects such as peeling deformation, cracks, and disconnection when the mold is released from the mother mold can be suppressed. Moreover, the effect which suppresses the crack and disconnection at the time of releasing mold materials, such as glass paste, from a shaping | molding die at a post process is also acquired.

  (B) The urethane compound preferably has a weight average molecular weight of 15,000 to 100,000. By setting the weight average molecular weight within this range, the flexibility and toughness of the mold can be made sufficient, and the compatibility of the curable resin composition for molds can be maintained. More preferably, it is 18000-80000.

Further, the (B) urethane compound is preferably represented by the following general formula (1).
R ^1- (R ² -R ³ ) _n -R ⁴ -R ⁵ (1)
(Here, R ¹ and R ⁵ are each selected from an organic group containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyalkyl group. R ² and R ⁴ are each an organic group containing a urethane bond, R ³ is an alkylene oxide chain, and n is a natural number of 1 to 10.
In general formula (1), R ¹ and R ⁵ were selected from any of a substituent containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyalkyl group. However, it is preferable that at least one of them is a substituent containing an ethylenically unsaturated group, and it is more preferable that both R ¹ and R ⁵ are substituents containing an ethylenically unsaturated group. By including an ethylenically unsaturated group, (A) a curable compound and a crosslinked structure are formed, and the effect of improving toughness and suppressing microlayer separation is also obtained. It is particularly preferable that the substituent containing an ethylenically unsaturated group is a (meth) acryl group.

R ³ is an alkylene oxide chain, but the molding compound can be made more flexible when the urethane compound contains an alkylene oxide chain. Further, by controlling the polarity of the alkylene oxide chain, the compatibility of the curable resin composition for molds can be easily improved. The alkylene oxide chain in propylene oxide chain of R ³ preferably contains 30 to 100 wt%. By containing a propylene oxide chain in this range, the flexibility is improved, the polarity of the urethane compound is lowered, the surface tension of the mold is reduced, and the molding material such as glass paste is attached to the mold. The effect of suppressing is acquired.

  Specific examples of urethane compounds preferably used in the present invention include UA-340P (molecular weight 42000), UA-340PM (molecular weight 42000), UA-2235PE (molecular weight 18000), UA-3238PE (molecular weight 19000), UA-3348PE ( Molecular weight 22000), UA-5348PE (molecular weight 39000) (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like, but are not limited thereto. Moreover, you may use these compounds in mixture.

  (B) It is preferable to contain 10 to 98 weight% of urethane compounds in the curable composition for molds. More preferably, it is 20 to 70% by weight. By making content into this range, the effect of a urethane compound can be made sufficient.

  The curable resin composition for a mold according to the present invention needs to contain (D) a surfactant. By containing a surfactant, the surface tension of the curable resin composition for molds can be reduced and the mold release can be improved, so the plasticity when releasing the curable resin composition for molds from the matrix Generation of defects such as deformation, peeling, and cracks can be suppressed. Furthermore, when the mold is released from the molding material such as glass paste in a later step, adhesion of the molding material to the mold can be suppressed, and defects such as plastic deformation, peeling, and cracks can be suppressed.

  (D) The surfactant is preferably a fluorine atom-containing surfactant. By using the fluorine atom-containing surfactant, the effect of reducing the surface tension of the mold can be greatly increased. As a result, when the mold is filled with the resin composition for mold according to the present invention and cured, the mold is easily separated from the mother mold, and defects such as plastic deformation, peeling and cracking of the mold are facilitated. Can be suppressed. Further, adhesion of a molding material such as glass paste in a subsequent process can be suppressed, and the occurrence of defects in the formed pattern can be greatly reduced. Furthermore, the surfactant preferably has an alkylene oxide chain, and is particularly preferably represented by the following general formula (2).

^{_{R 6 - [(CH 2)}} k O) l -R 7] m (2)
(Here, R ⁶ is an organic group having a valence of 1 to 4, R ⁷ is an organic group containing a fluorine atom, k is 2 to 4, l is 4 to 30, and m is a natural number of 1 to 4. Is)
In Formula (2), it is preferable that l is 4-30. By setting l to 4 to 30, compatibility with other organic components is improved, and the effect of reducing the surface tension by fluorine can be made sufficient.

  Specific examples of the (D) surfactant preferably used in the present invention include FTX-240D, FTX-220D, FTX-212D, and FTX-204F manufactured by Neos, but are not limited thereto. Is not to be done. These compounds may be used as a mixture.

  (D) It is preferable to contain 0.001 to 5 weight% of surfactant in the curable resin composition for molds. More preferably, it is 0.01-3 weight%. By setting the content in this range, the effect of reducing the surface tension can be made sufficient, and the adhesion between the support and the curable resin composition for the mold is not impaired.

  In the curable resin composition for a mold according to the present invention, (A) a curable compound is used. The curable compound is not particularly limited as long as it can be cured by energy such as light and heat. However, in order to form a pattern with high accuracy and a high aspect ratio, a photocurable compound is preferable, and in particular, It is preferably an acrylic monomer. By using a (meth) acrylic monomer, the mold can be made transparent, and when a photocurable composition is used as a molding material used for manufacturing a structure, photocuring of the molding material is easy. Can be done.

   Examples of the (meth) acrylic monomer include alcohols (for example, methanol, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc.) acrylic acid ester or methacrylic acid ester, carboxylic acid (for example, , Propionic acid, benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) with glycidyl acrylate, glycidyl methacrylate, amide derivatives (eg, acrylamide, Methacrylamide, N-methylolacrylamide, methylenebisacrylamide, etc.), and a reaction product of an epoxy compound with acrylic acid or methacrylic acid. , It is preferable to use a polyfunctional compound such as trifunctional. By using a polyfunctional compound, the curable resin composition for molds of the present invention can be efficiently crosslinked. Examples of such polyfunctional compounds include butanediol diacrylate, hexanediol diacrylate, nonanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, and polyethylene glycol diacrylate. , Propylene glycol diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, glycerin diacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, dimethylol-tricyclo Decane diacrylate, bisphenol A diacrylate, ethylene oxide Examples thereof include side-modified bisphenol A-diacrylate, propylene oxide-modified bisphenol A-diacrylate, and the like. Trifunctional or higher polyfunctional compounds include trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate (above, trifunctional compound), pentaerythritol tetraacrylate, ditrimethylol. Examples include propanetetraacrylate, (tetrafunctional compound), dipentaerythritol hexaacrylate (hexafunctional compound), and the like. In these polyfunctional compounds, some or all of the acrylic groups may be replaced with methacrylic groups. In the present invention, one or more of these can be used.

  (A) It is preferable that a curable compound is 1 to 90 weight% in the curable resin composition for molds. More preferably, it is 3 to 70% by weight. By setting the content within this range, the flexibility and toughness of the mold can be maintained within an appropriate range.

  The (C) polymerization initiator used in the present invention is preferably one that generates radical species by light irradiation or heat. As the polymerization initiator, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) ) Oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Ter, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ' , 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-Benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propenaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4- Dimethylthio Xanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl- 1-propanaminium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2-bi Imidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-Hexafluorophosphate (1-), diphenyl sulfide derivative, bis η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 4,4-bis (dimethylamino) benzophenone, 4 , 4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy 2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β- Chloranthraki , Anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2 -Phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, N-phenylglycine, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide and eosin, methylenebutene Examples include a combination of a photoreductive dye such as roux and a reducing agent such as ascorbic acid or triethanolamine.

  In the present invention, one or more of these can be used. It is preferable that a polymerization initiator is contained in 0.05-10 weight% in the curable resin composition for shaping | molding molds, More preferably, it is 0.1-10 weight%. By setting the content of the polymerization initiator in this range, it is possible to sufficiently increase the reaction rate of the curable resin composition for molds and at the same time obtain a sufficient degree of polymerization.

  The curable resin composition for molds of the present invention can contain a binder resin in addition to the above (A) to (D). By containing the binder resin, the curing stress at the time of curing can be further reduced. Examples of the binder resin include, but are not limited to, acrylic resin, cellulose resin, epoxy resin, melamine resin, phenol resin, urea resin, vinyl chloride resin, polyethylene, and polypropylene. An acrylic resin is particularly preferable from the viewpoints of compatibility, transparency, and flexibility. It is preferable that the glass transition point (henceforth Tg) of an acrylic resin is -50-50 degreeC, More preferably, it is 0-25 degreeC. By setting the Tg of the acrylic resin within this range, it becomes possible to achieve both ease of handling and flexibility. The content of the binder resin is preferably 0.1 to 50% by weight, more preferably 0.1 to 30% by weight in the curable resin composition for a mold. By setting the content within this range, the curable resin composition can be sufficiently cured, and at the same time, the mold can be softened and the curing stress at the time of curing can be sufficiently reduced.

  The curable resin composition for a mold according to the present invention preferably contains a plasticizer. By containing a plasticizer, the flexibility of the mold can be further improved. Plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, and dioctyl adipate. , Adipates such as dinonyl adipate and di-2-butoxyethyl adipate, azelaates such as dioctyl azelate, sepacate, tricresyl phosphate, tributyl acetylcitrate, epoxidized soybean oil, trimellitic ester Among them, a plasticizer containing one or more of these may be mentioned. From the viewpoint of safety, adipic acid esters, sepacic acid esters, and the like are preferable. The content of the plasticizer is preferably 0.1 to 70% by weight, more preferably 0.1 to 50% by weight in the curable resin composition for molds.

  The curable resin composition for molds of the present invention can further contain a solvent as necessary. As the solvent, commonly used solvents can be used. For example, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, benzyl alcohol, 3 -Methoxy-3-methyl-1-butanol, 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate, terpineol, butyl carbitol, butyl carbitol acetate, tetrahydrofuran, dimethyl sulfoxide, γ- Butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, etc. and organic solvent mixtures containing one or more of these are used. .

  The method for producing a mold according to the present invention includes a step of filling a matrix with the above-described curable resin composition for a mold, a step of curing the curable resin composition for a mold, and a step of removing the matrix. including.

  As a specific example, an example of a method for forming a mold used for forming a partition wall of a plasma display by using the curable resin composition for a mold according to the present invention will be described in detail.

  First, prepare the master mold. The mother mold has the same uneven shape as the desired partition wall, taking into consideration the shrinkage rate due to the curing of the curable resin composition for the mold and the shrinkage rate due to the curing and baking of the glass paste used to form the partition wall. Can be designed. The master mold can be made by cutting alloys such as steel, carbon steel, aluminum alloy, stainless steel, copper alloy, titanium alloy, and inorganic materials such as glass, but it can also be made by the photosensitive paste method. preferable. When producing by the photosensitive paste method, it can produce as follows, for example. First, a photosensitive paste composed of a photosensitive organic component and an inorganic component is applied to a substrate to a desired thickness, dried as necessary, and then exposed through an exposure mask to develop the unnecessary portion of the photosensitive paste. To obtain a pattern, and finally, the photosensitive organic component in the pattern is removed by baking to obtain a matrix made of only inorganic components.

  Next, the mold is filled with the cured resin for a mold according to the present invention. As a filling method, methods such as screen printing, knife coater, bar coater, roll coater, die coater, and blade coater can be used, and drying can be performed as necessary. The filling thickness can be determined in consideration of the desired partition wall height and the shrinkage ratio due to curing and baking of the curable resin composition. Usually, it is the range of 5-1000um, Preferably, it is the range of 30-800um. The filling thickness can be adjusted by the screen mesh, the viscosity of the curable resin composition, and the like. Drying is performed using a hot-air dryer, IR dryer, etc., and drying temperature and time can be adjusted with the solvent and coating film thickness of the curable resin composition used.

  Next, the support is pressure-bonded to a matrix filled with the curable resin composition. As the support, a polyethylene film, a polyvinyl chloride film, a polypropylene film, a polyester film, a polycarbonate film, a polystyrene film, or the like can be used. However, it is preferable that the support is flexible, tough and transparent. A highly transparent film is preferably used. The pressure-bonding method is not particularly limited, but when a laminating method using a laminating roll is used, a uniform film free from voids and bubbles can be obtained.

The curable resin composition for a mold is cured in a state where the support and the curable resin composition for a mold are pressed onto the mother die. In this application, it is preferable to make the curable resin composition for molds photocurable, and in this case, light irradiation is performed from the support side. Examples of the active light source used at this time include near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. Among these, ultraviolet rays are most preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, or a germicidal lamp can be used. The light irradiation conditions vary depending on the coating thickness, but are usually performed for 0.01 to 10 minutes using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² .

  Thereafter, the support and the cured resin are separated from the mother die to obtain a mold. The obtained mold is free from defects such as deformation, cracks and disconnection.

  FIG. 1 schematically shows an example of a method for forming a mold used for forming a partition wall of a plasma display using a photocurable mold-curable resin composition.

  First, as shown in FIG. 1 (a), a curable resin composition 4 a for a mold is disposed on a mother mold 1, a support 3 (PET film) is further disposed, and pressure bonding is performed using a laminate roll 2. By doing so, the mold 1 is filled with the curable resin composition 4a for the mold.

  Next, as shown in FIG.1 (b), the ultraviolet-ray 9 is irradiated from the support body 3 side, and the curable resin composition for molds is hardened. Furthermore, the mold 4b can be obtained as shown in FIG. 1C by peeling the curable resin composition for the mold that is cured from the matrix.

  Next, a method for forming a structure using the produced mold will be described in detail.

First, a molding material is prepared. The molding material is not particularly limited, but a material that can be filled in the mold and can hold the pattern after the mold is released is preferably used. A material that is cured by reaction with light or heat is more preferable, and in the case of forming a pattern with high accuracy and a high aspect ratio, it is particularly preferable to use a photosensitive composition that is cured by light. When the mold produced according to the present invention is transparent, a highly accurate and high aspect ratio pattern can be quickly formed with a small exposure by using the photosensitive composition. In order to provide photosensitivity, it is achieved by containing a curable compound and a photopolymerization initiator. When forming a glass structure using this invention, the glass paste which consists of an inorganic component containing an organic component and glass is used for a molding material. An example of the molding material is shown below.
Curing compound: polyethylene glycol diacrylate (3 to 20% by weight)
Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (0.05 to 10% by weight)
Surfactant: F-containing surfactant (0 to 10% by weight)
Solvent: γ-butyrolactone (0-30% by weight)
Inorganic particles: A mixture of low softening point glass and ceramic filler (40 to 97% by weight)
Subsequently, a molding material is applied to the substrate. As a coating method, it can apply | coat using methods, such as screen printing, a bar coater, a roll coater, a die coater, a blade coater, and can be dried as needed. The coating thickness can be determined in consideration of the desired structure height and the shrinkage of the molding material. The coating thickness can be adjusted by the number of coatings, the screen mesh, the viscosity of the molding material, and the like. Drying is performed using a hot air dryer, IR dryer, or the like, and the drying temperature and time can be adjusted by the solvent of the molding material used and the coating film thickness.

  Next, the molding die of the present invention is pressure-bonded onto the molding material coating film. The pressure-bonding method is not particularly limited, but when a laminating method using a laminating roll is used, a uniform film free from voids and bubbles can be obtained.

In the case of using a photocurable molding material, light irradiation can be performed in a state where the molding die is pressure-bonded to the molding material. Examples of the active light source used at this time include near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. Among these, ultraviolet rays are most preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, or a germicidal lamp can be used. Although light irradiation conditions differ with application | coating thickness, it is normally performed for 0.01 to 30 minutes using the ultrahigh pressure mercury lamp of the output of 1-100 mW / cm < ² >.

  Thereafter, the mold is removed from the molding material coating film to obtain a desired structure. The obtained structure is free from defects such as deformation, cracks and disconnection. When firing in a later step, the mold can be removed by firing.

  Subsequently, particularly when a glass paste is used as the molding material, it can be fired in a firing furnace. The firing atmosphere and temperature vary depending on the molding material and the type of substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace, a belt-type continuous firing furnace, or the like can be used, and firing is performed at a temperature of 350 to 800 ° C., preferably 520 to 620 ° C. for 1 to 60 minutes. Further, as described above, firing can be performed without separating the mold from the molding material. In the case where the mold is composed only of organic components, the mold can be removed from the molding material by firing.

  The present invention can be particularly preferably applied to a method for producing a display member, in which case a step of filling a glass paste between a substrate and a mold produced by the above-described method, firing at a temperature of 350 to 800 ° C. The partition wall is formed by a manufacturing method including the step of:

  FIG. 2 schematically shows an example of a method for forming the partition walls of the plasma display using the above-described partition wall forming mold and photocurable glass paste.

  First, as shown in FIG. 2A, a substrate 10 provided with a stripe-shaped address electrode 6 and a dielectric layer 7 covering the address electrode 6 on a glass substrate 5 is prepared. Glass paste 8a is applied. Next, the above-described molding die 4b is placed and pressed using the laminating roll 2 to fill the glass paste 8a between the substrate 10 and the molding die 4b.

  Next, as shown in FIG. 2 (b), the glass paste 8a is cured by irradiating ultraviolet rays 9 from the mold 4b side, and then the mold 4b is peeled off from the substrate 10 and the cured glass paste, and then FIG. A substrate 10 having a partition wall pattern 8b as shown in FIG. Further, by baking this, a member for plasma display having the partition walls 8c can be obtained.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to this. A 42-inch plasma display having 2.70 million pixels was manufactured using the present invention.
The raw materials used for the curable resin composition for molds are as follows.
Curing compound I: 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
Curing compound II: Tetrapropylene glycol diacrylate (manufactured by NOF Corporation)
Urethane compound I: Urethane diacrylate (“NA-340P” manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 42000)
Urethane compound II: Urethane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. “UA-2235PE”, molecular weight 18000)
Urethane compound III: Urethane dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. “UA-340PM”, molecular weight 42000)
Urethane compound IV: Urethane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. “UA-4120P”, molecular weight 13000)
Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (“IC369” manufactured by Ciba Specialty Chemicals)
Surfactant I: F-based surfactant ("FTX-240D" manufactured by Neos Co., Ltd., ethylene oxide chain repeating unit 10)
Surfactant II: F-based surfactant (“FTX-220D” manufactured by Neos Co., Ltd., ethylene oxide chain repeating unit 10)
Surfactant III: F-based surfactant (“FTX-212D” manufactured by Neos Co., Ltd., ethylene oxide chain repeating unit 10)
Surfactant IV: Si-based surfactant (“BYK-3700” manufactured by Big Chemie)
Binder resin: Acrylic polymer ("MM-2002" manufactured by Fujikura Kasei Co., Ltd.)
A. Preparation of curable composition for molds The curable composition for molds was prepared as follows.

  A predetermined amount of a curable compound, a urethane compound, a surfactant, a polymerization initiator (0.5% by weight), a binder resin (10% by weight), and a plasticizer (30% by weight) is weighed, and then a solvent is added as appropriate to increase the viscosity. Was prepared by heating and stirring to obtain a curable composition for a mold. Table 1 shows the amounts of the curable compound, the urethane compound, and the surfactant used in each example and comparative example.

B. Preparation of mother mold A negative photosensitive paste method was used for the fabrication of the mother mold. First, a negative photosensitive organic component composed of a negative photosensitive organic component and an inorganic component including a low softening point glass is applied to a substrate to a desired thickness, dried, then exposed through an exposure mask, and developed. The pattern is obtained by removing the photosensitive paste from the uncured part, and finally the photosensitive organic component in the pattern is removed by baking at 600 ° C. for 15 minutes, and the glass is softened to form a matrix made of only inorganic components. Obtained. The fabricated master has a stripe-shaped main partition (pitch 160 μm, top line width 50 μm, bottom line width 80 μm, height 120 μm) and a stripe-shaped auxiliary partition (pitch 800 μm, top line width 80 μm). , Having a grid-like partition wall pattern having a bottom line width of 100 μm and a height of 110 μm.

C. Production of Mold Using the produced mold curable composition, a mold was produced according to the following procedure.

The curable composition for molds was uniformly filled into the mother mold by blade coating. Subsequently, a support (PET film, “Lumirror” manufactured by Toray Industries, Inc.) was placed on the mother mold, and uniformly bonded using a laminate roll. The film thickness was about 300 μm at the concave portion (position on the convex portion of the matrix). The substrate was exposed to ultraviolet rays for 20 seconds with an ultrahigh pressure mercury lamp with 50 mW / cm ² output from the support surface in a state where the support was pressure-bonded to the mother mold through the curable composition for a mold. Thereafter, the support and the cured curable composition for a mold were peeled from the mother mold to obtain a mold having irregularities opposite to the desired partition wall shape. The obtained mold was observed for cracks, disconnections, and peeling from the support. Mold crack evaluation is AA if cracks, breakage and peeling from support are 1 or less, mold evaluation is A if 2-5, mold evaluation is B if 6-19, and 20 or more Then, it was impossible as a mold, and C was used.

D. Method for Producing Plasma Display Partition Wall Using the prepared mold, a plasma display partition wall was produced by the following procedure. An address electrode pattern having a pitch of 160 μm and a line width of 50 μm was formed on a “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd. by photolithography using a photosensitive silver paste. Next, a dielectric layer having a thickness of 20 μm was formed on the glass substrate on which the address electrodes were formed by screen printing. Thereafter, a glass paste having the composition shown below was uniformly applied on the back plate glass substrate on which the address electrode pattern and the dielectric layer were formed by a die coating method so as to have a thickness of 100 μm.
(Composition of glass paste)
Curing compound: Tetraethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) 4.5% by weight
・ Curable compound: EO-modified bisphenol A diacrylate (manufactured by NOF Corporation) 5% by weight
Polymerization initiator: bis (2,4,6-trimethylbenzoy) -phenylphosphine oxide (manufactured by Ciba Specialty Chemicals) 1% by weight
・ Dispersant: Nonyl ether dispersant 1% by weight
・ Solvent: 9.5% by weight of γ-butyrolactone
・ Inorganic particles: Mixture of low softening point glass and ceramic filler 80% by weight
Subsequently, the above-described mold was pressed against the glass paste by a laminating method using a laminating roll. The glass substrate, the dielectric layer, and the electrode were used, and the substrate was exposed to ultraviolet rays for 20 seconds with an ultrahigh pressure mercury lamp with an output of 50 mW / cm ² from the mold surface while the support was pressed against the substrate. Thereafter, the mold was peeled off from the partition glass paste to obtain a partition pattern having a desired partition shape. Then, the partition was formed by hold | maintaining for 30 minutes and baking at 560 degreeC. The obtained partition walls were observed for cracks, disconnections, and height unevenness. If the crack, breakage, and height unevenness are 1 or less, the partition evaluation is AA, if 2 to 5 locations, the partition evaluation is A, if 6 to 19 locations, the partition evaluation is B, and if 20 locations or more, the partition is not possible. And C.

E. Method for Producing Plasma Display A phosphor layer was formed to a thickness of 20 μm on the obtained substrate with barrier ribs by a dispenser method and baked to obtain a plasma display back plate.

  Subsequently, a plasma display front plate was produced by the following procedure. An ITO electrode having a thickness of 1 μm was formed on a “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd. by a photoetching method, and then a bus electrode pattern was formed by a photolithography method using a photosensitive silver paste. . Thereafter, a transparent dielectric layer was formed to a thickness of 30 μm by screen printing. Finally, a 500 nm thick MgO film was formed by electron beam evaporation to obtain a front plate.

  After sealing the produced front plate and back plate, a noble gas of xenon-neon mixed gas of 5% by volume of xenon is sealed in a space formed between the front and back substrates at a pressure of 450 mmHg, thereby plasma display A panel portion was prepared. In addition, a plasma display having 2.70 million pixels was fabricated by mounting a driver IC for driving. The obtained plasma display was turned on every other row along the partition wall direction, and was visually evaluated for lighting, non-lighting, or flickering due to erroneous discharge. The evaluation is AA if the number of lit cells or unlit cells due to erroneous discharge is 1 or less, A is evaluation if 2-5, display evaluation B is 6-19, display evaluation B, 20 If it is more than one, it is not possible as a display panel, and C is used. When only flickering occurred, the display evaluation was A.

Example 1
When a mold was produced using the curable resin composition for molds shown in Table 1, a mold having a good shape and no defects such as deformation, cracks, and disconnection was obtained, and the mold evaluation was AA. It was. The partition for plasma display produced using the obtained shaping | molding die had a favorable shape, there was no defect, partition evaluation was AA, and when the plasma display was produced, display evaluation was also AA.

(Example 2)
Example 1 was repeated except that 50% by weight of urethane compound II was added to the urethane compound and surfactant II was used as the surfactant. The obtained mold, the partition for plasma display, and the plasma display were good with no defects, and all were evaluated as AA.

(Example 3)
Example 1 was repeated except that urethane compound III was used as the urethane compound. The obtained mold, the partition for plasma display, and the plasma display were good with no defects, and all were evaluated as AA.

Example 4
Example 1 was repeated except that urethane compound IV was used as the urethane compound. Since the flexibility of the mold was insufficient, 12 cracks occurred when the mold was released from the mold, and the mold evaluation was B. The partition for plasma display produced using the obtained shaping | molding die similarly produced 12 defects, the plasma display also had 12 unlit cells, and all were evaluation B.

(Example 5)
Example 1 was repeated except that the amount of surfactant I added was 0.005% by weight. The obtained mold had a good shape with no defects, and the mold evaluation was AA. However, when the partition for plasma display was produced using the obtained mold, the mold releasability was insufficient. Therefore, four disconnections occurred and the partition evaluation was A. The plasma display also had four unlit cells, and the display evaluation was A.
(Example 6)
Example 1 was repeated except that the addition amount of the surfactant I was changed to 5% by weight. When the mold was released from the mother die, the adhesion with the support decreased, and partly peeled off from the support. The partition for plasma display produced using the obtained shaping | molding die flickered at the time of plasma display lighting since the partition height differs partially in the peeling generation | occurrence | production part of a shaping | molding die. The molding die, partition wall, and display evaluation were all A.
(Example 7)
Example 1 was repeated except that surfactant III was used as the surfactant. The curable resin composition for molds was opaque and was not sufficiently uniform. The obtained mold had a good shape with no defects, and the mold evaluation was AA. However, when the partition for plasma display was produced using the obtained mold, the mold releasability was partially Inadequate, 3 breaks occurred. The plasma display also had three unlit cells, and both the partition wall and display evaluation were A.
(Example 8)
Example 1 was repeated except that surfactant IV was used as the surfactant. When the mold was released from the mother mold, the mold release from the mother mold was insufficient and seven breaks occurred, and the mold evaluation was B. When producing the partition for plasma displays using the obtained shaping | molding die, since the mold release property of the shaping | molding die was inadequate, disconnection generate | occur | produced further and the disconnection became 12 places. The plasma display also had 12 unlit cells, and the partition and display evaluation were both B.
(Comparative Example 1)
Example 1 was repeated except that no urethane compound was added. The flexibility of the mold was extremely insufficient, and 20 or more cracks occurred during release from the mother mold. The partition for plasma display produced using the obtained shaping | molding die produced 20 or more defects, the plasma display also had 20 or more unlit cells, and all were evaluated as C.
(Comparative Example 2)
Example 1 was repeated except that no surfactant was added. When the mold was released from the mother die, the releasability from the mother die was extremely insufficient and disconnections occurred at 20 or more locations. When producing the partition for plasma display using the obtained mold, since the mold releasability is extremely insufficient, further disconnection occurs, and the plasma display has more than 20 unlit cells. Both were C.

It is the figure which showed typically an example of the method of forming the shaping | molding die used for the partition formation of a plasma display by this invention. It is the figure which showed typically an example of the method of forming the partition of a plasma display by this invention.

Explanation of symbols

1: Matrix
2: Laminate roll 3: Support 4a: Curable resin composition 4b: Mold 5: Glass substrate 6: Address electrode 7: Dielectric layer 8a: Glass paste 8b: Partition pattern 8c: Partition 9: Ultraviolet 10 :substrate

Claims (8)

A curable resin composition for a mold, comprising at least (A) a curable compound, (B) a urethane compound, (C) a polymerization initiator, and (D) a surfactant. The weight average molecular weight of (B) urethane compound is 15000-100,000, The curable resin composition for molds of Claim 1 characterized by the above-mentioned. (B) The curable resin composition for molding dies according to claim 1, wherein the urethane compound is represented by the following general formula (1).
R ^1- (R ² -R ³ ) _n -R ⁴ -R ⁵ (1)
(Here, R ¹ and R ⁵ are each selected from an organic group containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyalkyl group. R ² and R ⁴ are organic groups, at least one is an organic group containing a urethane bond, R ³ is an alkylene oxide chain, and n is a natural number of 1 to 10.) (D) Surfactant is a fluorine atom containing surfactant, The curable resin composition for molds of Claims 1-3 characterized by the above-mentioned. (D) Surfactant is represented by following General formula (2), The curable resin composition for molds of Claim 4 characterized by the above-mentioned.
_{^{R 6 - [(CH 2)}} k O) l -R 7] m (2)
(Here, R ⁶ is an organic group having a valence of 1 to 4, R ⁷ is an organic group containing a fluorine atom, k is 2 to 4, l is 4 to 30, and m is a natural number of 1 to 4. .) A step of filling the mold with the curable resin composition for a mold according to any one of claims 1 to 5, a step of curing the curable resin composition for a mold, and a step of removing the matrix. The manufacturing method of the shaping | molding die characterized by this. A method for producing a structure, comprising a step of filling a molding die produced by the method for producing a molding die according to claim 6 and a step of removing the molding die. Forming a partition wall by a manufacturing method including a step of filling a glass paste between the substrate and a forming die produced by the manufacturing method of a forming die according to claim 6 and a step of baking at a temperature of 350 to 800 ° C. A method for producing a display member.

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