KR101486641B1 - Photosensitive resin composition, photosensitive element comprising the composition, method for formation of septum for image display device, process for production of image display device, and image display device - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming a partition wall separating pixels in an image display apparatus having bendability provided with at least a transparent electrode on a display surface, wherein the photosensitive resin composition comprises (A) component: a binder having a carboxyl group in the molecule (B) component: a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a component: a compound having an epoxy group in the molecule, wherein the photosensitive resin composition is photo- And an elongation at 25 캜 of a cured product of a sheet having a width of 10 mm and a thickness of 45 탆, which is obtained by heating for 1 hour, at 40% or more.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method of forming a partition of an image display device, a method of manufacturing an image display device, and an image display device. FOR PRODUCTION OF IMAGE DISPLAY DEVICE, AND IMAGE DISPLAY DEVICE}

The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method of forming a partition wall of an image display apparatus, a method of manufacturing an image display apparatus, and an image display apparatus.

2. Description of the Related Art Recently, an image display device (PLD: Paper Like Display), which is thin like paper, is portable, and can display characters and images, is attracting attention. Such an image display device has visibility and portability, which are advantages of paper as a normal printed matter, and can be rewritten electrically. Therefore, practical use as a substitute for paper has been attempted in terms of environment and cost.

As the display technology of the image display device, various types such as a type for moving particles by electrophoresis or the like, a liquid crystal type, and an electrochemical type have been devised (for example, see Non-Patent Document 1). Particularly, as methods for moving particles, methods such as a microcapsule electrophoresis method, a microcup electrophoresis method, an electronic powder fluid method, and a toner display method have been studied. In these methods, white and black particles, which are display media, are sealed between transparent electrodes to apply an electric field, and these particles are electrically moved to form a white / black image to be displayed. In addition, as the driving method of the image display apparatus, there are active driving and passive driving, and the back surface technology (panel circuit) for the image display apparatus is also studied.

In the case of the image display apparatus of the particle movement type, a partition wall for enclosing white / black particles is required as described above. As methods for forming such barrier ribs, a metal mold transfer method, a screen printing method, a sandblast method, a photolithography method, an additive method, and the like have been proposed (see, for example, Patent Document 1). Among them, a photolithography method capable of efficiently forming a high-precision pattern by irradiation of an actinic ray using a photosensitive resin composition has attracted attention.

In recent years, there has been a report (for example, see Non-Patent Document 2) that full color display is realized by examining the flexibility of the image display apparatus and combining color filters for white / black image display.

When the image display apparatus is made flexible, the flexibility of the electrode substrate is essential. In recent years, substitution products of ITO such as IZO (indium zinc oxide), Ag wire / ink, and organic conductive material have been studied (for example, ITO (Indium Tin Oxide) See, for example, Non-Patent Document 3). Various degrees of flexing have been studied to such an extent that it is possible to bend it to a degree of flexibility, and it is rounded to be small so that the volume can be reduced at the time of carrying. The radius of curvature in the case of small rounding is generally assumed to be about 15 to 20 mm, which is the limit of the bending property of the ITO electrode substrate. However, in the Ag wire / ink or organic conductive material and combinations thereof, The radius can be reduced.

In addition, when full-color display is performed, the color filter is used in combination with the image display apparatus for white / black display, so that it is necessary to improve the contrast between the pixels. Therefore, a light shielding layer for shielding light between the pixels is required. In the case of the monochrome display, since the brightness of the image of the image display device is increased without using a color filter, transparency is required instead of light shielding.

The partition walls of the image display apparatus using the photolithography method are formed as follows. A step of laminating a light-shielding layer called a black matrix on a substrate by a photolithography technique; a step of applying a photosensitive resin composition on the light-shielding layer or laminating photosensitive elements to form a photosensitive resin composition layer; A step of irradiating a predetermined portion of the resin composition layer with an actinic ray to photo-cure the exposed portion, and a step of removing the unexposed portion to form a photo-curable pattern. Further, the light-shielding layer called a black matrix may be omitted. Therefore, the photosensitive resin composition for forming the barrier ribs of the image display device is generally required to have sensitivity, resolution, and adhesion to a substrate.

Further, in the case of manufacturing an image display apparatus, the method further includes a step of filling a display medium such as particles in the photo-curable pattern obtained in the above step, a step of heat-treating the photo-curable pattern, and a step of pasting the electrode substrate. Thus, an image display device using a cured product of the photosensitive resin composition layer as a partition wall is obtained.

Japanese Patent Laid-Open No. 2007-178881

 Suzuki Akira, "Recent Trend of Electronic Paper 2007 ", October 10, 2007, Journal of the Japan Institute of Invention and Innovation Society of Japan, vol.46 No. 5: 372-384 (2007)  &Quot; Flexible electronic paper using an electronic powder fluid ", October 10, 2007, Japan Inverter Science Journal Vol. 46, No. 5: 396-400 (2007)  Nezu Tadashi, "Introduction of new materials to transparent electrodes", August 10, 2009, Nikkei Electronics 59-65 (2009)

In the step of affixing the electrode substrate, a voltage is applied under high temperature and high humidity, and there is a possibility that an electrode portion in close contact with the cured product of the photosensitive resin composition is dissolved. In fact, since IZO, which is studied as a flexible electrode substrate, contains an amphoteric zinc, there has been a problem that it is dissolved in the step of attaching the electrode substrate. When an electrode material having a high degree of bending property and capable of coping with a radius of curvature of about 5 to 15 mm, for example, an Ag wire / ink or an organic conductive material, or a combination thereof is used, .

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a photosensitive resin composition capable of forming a partition wall capable of suppressing dissolution of electrodes and suppressing breakage at the time of bending, A method of forming a barrier rib, a method of manufacturing an image display device, and an image display device.

In order to achieve the above object, the present invention is a photosensitive resin composition for forming a partition wall separating pixels in an image display apparatus having bendability having at least a transparent electrode on a display surface, wherein the photosensitive resin composition comprises (A) : A binder polymer having a carboxyl group in a molecule, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a component: a compound having an epoxy group in the molecule, And a stretched sheet-shaped cured product having a width of 10 mm and a thickness of 45 占 퐉, which is obtained by heating the sheet at 120 占 폚 for 1 hour in air, at an elongation at 25 占 폚 of 40% or more.

According to the photosensitive resin composition having the above-described structure, it is possible to form a partition wall capable of suppressing breakage at the time of bending while suppressing dissolution of the electrode, which is a problem in forming the partition wall of the image display apparatus. Further, according to the photosensitive resin composition, an optical photocured pattern having excellent resolution and adhesion can be formed with high sensitivity. The reason why the dissolution of the electrode is inhibited by the photosensitive resin composition having the above-described structure is not clear, but it is considered that the dissolution of the electrode is suppressed by trapping the carboxyl group remaining in the cured product of the photosensitive resin composition by the component (D) . The breakage of the barrier rib at the time of bending is suppressed by adjusting the elongation of the cured product of the photosensitive resin composition so as to be in the above range so that the barrier rib can follow the elongation at the time of bending of the image display device . According to the photosensitive resin composition of the present invention, even when the image display device is bent at a radius of curvature of about 5 to 15 mm, a partition wall capable of sufficiently preventing breakage can be formed.

The photosensitive resin composition of the present invention may further contain a component (E): an inorganic black pigment. The component (E) preferably contains titanium black. By containing such component (E), it is possible to balance property of light sensitivity and light shielding property. On the other hand, in order to improve the brightness of the image display device, there is a case that a photosensitive resin composition for forming a barrier rib which does not contain any of the inorganic black pigment (component (E) May be added as needed.

The present invention also provides a photosensitive element comprising a support and a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention formed on the support. By using such a photosensitive element, it is possible to form a partition wall capable of suppressing breakage at the time of bending while suppressing dissolution of the electrode, which is a problem in forming the partition of the image display apparatus. Further, according to such a photosensitive element, a photocured pattern having excellent resolution and adhesion can be formed with high sensitivity.

The present invention also provides a method of forming a barrier rib of an image display apparatus having flexibility, which has at least a transparent electrode arranged on a display surface and a partition wall separating pixels, A step of laminating a photosensitive resin composition layer made of a photosensitive resin composition, an exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to cure the exposed portion, and a step of exposing the photosensitive resin composition layer And a developing step of forming a photocured product pattern by removing the photocatalytic pattern.

The present invention also provides a manufacturing method of a flexible image display device having at least a transparent electrode arranged on a display surface and a partition wall separating the pixels, A manufacturing method of an image display device having a step of forming a barrier rib is provided.

According to the method of forming the partition walls of the image display apparatus and the method of manufacturing the image display apparatus, since the partition walls are formed by the photosensitive resin composition of the present invention, dissolution of the electrodes at the time of forming the partition walls is suppressed, It is possible to form a partition wall capable of suppressing breakage at the time of bending.

In the method of manufacturing the image display device, it is preferable that the transparent electrode is made of a material formed by applying a solution containing at least one kind of metal conductive fiber. This makes it possible to form an image display device having excellent bendability that can cope with a radius of curvature of about 5 to 15 mm. Examples of the electrode material include Ag wire, ink and the like.

It is preferable that the manufacturing method of the image display apparatus further includes a step of filling the display medium in the partition wall and a step of attaching the substrate to the opposite side of the partition wall so as to face the one substrate.

The present invention also provides an image display device manufactured by the above-described manufacturing method. Since these image display devices are manufactured by the above-described manufacturing method, they are provided with barrier ribs capable of suppressing the dissolution of the transparent electrodes and suppressing breakage at the time of bending, thereby improving the reliability of the device.

According to the present invention, there is provided a photosensitive resin composition capable of forming barrier ribs for an image display device capable of suppressing breakage at the time of bending while suppressing dissolution of electrodes when a voltage is applied under high temperature and high humidity, a photosensitive element using the same, A method of forming a partition wall of a display apparatus, a method of manufacturing an image display apparatus, and an image display apparatus can be provided.

1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention.
2 is a schematic cross-sectional view for explaining an embodiment of a method of forming a partition of an image display apparatus using the photosensitive element of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or equivalent portions are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratios in the drawings are not limited to the illustrated ratios. (Meth) acrylate in the present specification means acrylic acid and corresponding methacrylic acid, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl means acrylate and acrylic acid Yl and corresponding methacryloyl.

(Photosensitive resin composition)

The photosensitive resin composition of the present invention is a photosensitive resin composition for forming a partition for separating a pixel in an image display apparatus having bending property having at least a transparent electrode on a display surface, the composition comprising (A) a binder polymer having a carboxyl group in the molecule , The component (B): a photopolymerizable compound, the component (C): a photopolymerization initiator, and the component (D): a compound having an epoxy group in the molecule. The photosensitive resin composition is photo- Time elongation at 25 ° C of a cured product of a sheet having a width of 10 mm and a thickness of 45 μm, which is obtained by heating for a time of 40% or more.

Hereinafter, each component usable in the photosensitive resin composition of the present invention will be described in detail.

(A): a binder polymer having a carboxyl group in a molecule

The component (A) that can be used in the present invention is not particularly limited as long as it has a carboxyl group in the molecule and can impart film properties, and examples thereof include acrylic resins, styrene resins, epoxy resins, amide resins, Based resin, an alkyd-based resin, a phenol-based resin, and a urethane-based resin. Among them, an acrylic resin is preferable from the viewpoint of alkali developability. These may be used alone or in combination of two or more. Examples of combinations of two or more kinds of binder polymers include two or more kinds of binder polymers having different copolymerization components, two or more kinds of binder polymers having different weight average molecular weights, and two or more kinds of binder polymers having different degrees of dispersion. A polymer having a multimode molecular weight distribution described in Japanese Patent Application Laid-Open No. 11-327137 may also be used. Further, if necessary, the binder polymer may have a photosensitive group.

The component (A) can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. As the polymerizable monomer, for example, styrene; Polymerizable styrene derivatives such as vinyltoluene,? -Methylstyrene, p-methylstyrene and p-ethylstyrene; Acrylamide; Acrylonitrile; Esters of vinyl alcohols such as vinyl-n-butyl ether; (Meth) acrylic acid alkyl ester, (meth) acrylate tetrahydrofurfuryl ester, (meth) acrylate dimethylaminoethyl ester, (meth) acrylate diethylaminoethyl ester, (meth) acrylate glycidyl ester, 2,2,2 (Meth) acrylic acid,? -Bromo (meth) acrylic acid,? -Chlor (meth) acrylate, (meth) acrylic acid monomers such as? -furyl (meth) acrylic acid and? -styryl (meth) acrylic acid; Maleic acid; Maleic acid monoesters such as maleic acid anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester and maleic acid monoisopropyl ester; Fumaric acid, cinnamic acid,? -Cyanosinic acid, itaconic acid, crotonic acid and propiolic acid. As the polymerizable monomer having a carboxyl group, (meth) acrylic acid is preferable from the viewpoint of developability and stability. These may be used alone as a homopolymer or as a copolymer in combination of two or more.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof.

As the component (A), an acrylic copolymer containing methacrylic acid, methyl methacrylate, and butyl methacrylate is preferable in terms of developing property and resolution.

The acid value of the component (A) is preferably 30 mgKOH / g or more, more preferably 80 mgKOH / g or more, still more preferably 130 mgKOH / g or more, and particularly preferably 180 mgKOH / g or more. It is preferably 250 mgKOH / g or less, more preferably 240 mgKOH / g or less, still more preferably 230 mgKOH / g or less, and particularly preferably 220 mgKOH / g or less. In the case of developing with a solvent as the developing step, it is preferable to suppress the use of the polymerizable monomer having a carboxyl group.

Here, the acid value can be measured in the following manner. That is, first, about 1 g of a solution of a resin whose acid value is to be measured is determined, 30 g of acetone is added to this resin solution, and this is uniformly dissolved. Then, an appropriate amount of phenolphthalein, which is an indicator, is added to the solution, and titration is performed using a 0.1N KOH aqueous solution. Then, the acid value is calculated by the following formula.

Wherein W represents the mass (g) of the measured resin solution, I represents the mass (g) of the resin solution measured, and I represents the mass (% By mass) of the nonvolatile matter.

The weight average molecular weight of the component (A) (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) is preferably 20,000 or more, more preferably 25,000 or more, More preferably 30,000 or more. From the viewpoint of shortening the developing time, it is preferably 300,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less. The weight average molecular weight of the binder polymer is measured by a gel permeation chromatography method and is converted by using a calibration curve of standard polystyrene. Measurement conditions of the gel permeation chromatography (GPC) are as follows.

[Conditions for measuring GPC]

Pump: Hitachi L-6000 model (manufactured by Hitachi, Ltd.)

Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (all three) (trade name, product of Hitachi Kasei Kogyo Co., Ltd.)

Eluent: tetrahydrofuran

Measuring temperature: 25 ° C

Flow rate: 2.05 mL / min

Detector: Hitachi L-3300 Model RI (manufactured by Hitachi, Ltd.)

The content of the component (A) in the photosensitive resin composition is preferably not less than 40 parts by mass, more preferably not less than 45 parts by mass, in view of excellent coatability of the photosensitive resin composition to 100 parts by mass of the total of the components (A) and (B) Is more preferable. It is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the total amount of the component (A) and the component (B).

(B) Component: Photopolymerizable compound

Examples of the component (B) that can be used in the present invention are not particularly limited as long as photo-crosslinking is possible. For example, a component (B1): a compound having an ethylenic unsaturated group and a urethane bond in the molecule, a component (B2) And / or a compound obtained by reacting a glycidyl group-containing compound with an?,? - unsaturated carboxylic acid; and (B3): a compound having one ethylenic unsaturated bond in its molecule.

(B1): a compound having an ethylenic unsaturated group and a urethane bond in a molecule

It is preferable to include the component (B1) in that the elongation of the cured product can be improved and the adhesion to the flexible substrate is excellent.

The component (B1) that can be used in the present invention is not particularly limited, but preferably contains a compound having an isocyanuric ring structure. Examples of the compound having an isocyanuric ring structure include compounds represented by the following formula (1).

Formula (1) of, R ¹ are each to independently a group represented by the formula (2) below, or shown by the formula (3), or to represent a group represented by the formula (4), at least one of R ¹ is A group represented by the following formula (4)

[In the formula (2), R ² represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 15)

[In the formula (3), m is an integer of 1 to 15)

[Wherein R ² represents a hydrogen atom or a methyl group, n represents an integer of 1 to 9, and m represents an integer of 1 to 15]

From the viewpoints of the elastic modulus and the adhesion, at least two of R ¹ in the formula (1) are more preferably a group represented by the formula (4), and it is more preferable that all of R ¹ are groups represented by the formula (4).

It is preferable that m is an integer of 1 to 6 in chemical formula (2), (3) and (4). Further, in the formula (4), m is preferably an integer of 3 to 6 in view of excellent mechanical strength.

A compound represented by the above formula (1), as commercially available, for example, NK oligo UA-21EB (of Shin-Nakamura Kagaku Kogyo whether or sikki Kaisha, trade name, formula (1), R ¹ are both the general formula (4) Phosphorus compounds).

Examples of the component (B1) include a urethane compound having a urethane bond derived from the reaction of a terminal hydroxyl group of a polycarbonate compound and / or a polyester compound with an isocyanate group of a diisocyanate compound and having an isocyanate group at a plurality of ends, , A compound having a hydroxyl group and a compound having an ethylenic unsaturated group can be obtained by condensation reaction.

These compounds may be synthesized by conventional methods or commercially available ones. Examples of commercially available products include UF-8003M, UF-TCB-50, UF-TC4-55 (available from Kyoeisha Chemical Co., Ltd.), HT9082-95 (trade name, available from Hitachi Kasei Kogyo Co., ).

Examples of other components (B1) include (meth) acrylic monomers having a hydroxyl group at the? -Position and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1 , And 6-hexamethylene diisocyanate; EO-modified urethane di (meth) acrylate, EO and PO-modified urethane di (meth) acrylate. As the EO-modified urethane di (meth) acrylate, for example, UA-11 under the trade name of Shin Nakamura Chemical Co., Ltd. may be mentioned. Examples of the EO and PO modified urethane di (meth) acrylate include UA-13 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

(B2): A compound obtained by reacting an?,? - unsaturated carboxylic acid with a polyhydric alcohol and / or glycidyl group-containing compound

Examples of the component (B2) include polyethylene glycol di (meth) acrylate (having 2 to 14 ethylene groups), polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups Polyalkylene glycol di (meth) acrylate; (Meth) acrylates such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxy tri (meth) acrylate and trimethylol propane propoxytri (meth) ) Acrylate compounds; Tetramethylolmethane (meth) acrylate compounds such as tetramethylolmethane tri (meth) acrylate and tetramethylolmethane tetra (meth) acrylate; Dipentaerythritol (meth) acrylate compounds such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Bisphenol A dioxyethylene di (meth) acrylate such as bisphenol A dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, and bisphenol A decaoxyethylene di (meth) acrylate; Trimethylolpropane triglycidyl ether triacrylate, and bisphenol A diglycidyl ether acrylate.

Among them, polyalkylene glycol di (meth) acrylate is preferably used as the component (B2) in view of excellent resolution and adhesiveness while maintaining the low elasticity of the cured film. (7) is more preferable.

In the formula (5), (6) or (7), each R independently represents a hydrogen atom or a methyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group. n ₁ , n ₂ , n ₃ and n ₄ represent the number of repeating structural units comprising an oxypropylene group, and m ₁ , m _2, m ₃ and m ₄ represent the number of repeating structural units consisting of oxyethylene groups, repetition of the group total number m ₁ + m _2, m ₃ and m ₄ are each independently one to represent the 30 integer, and repeating the total number of oxypropylene groups n _1, n ₂ + n ₃ and n ₄ is to 1, each independently Lt; / RTI >

In the compound represented by the general formula (5), (6) or (7), the repeating total number m ₁ + m ₂ , m ₃ and m ₄ of the oxyethylene group are each independently an integer of 1 to 30, More preferably an integer of 4 to 9, and still more preferably an integer of 5 to 8. In view of excellent resolution and adhesion, the total number of these repeating numbers is preferably 10 or less, more preferably 9 or less, and even more preferably 8 or less.

The repeating total numbers n ₁ , n ₂ + n ₃ and n ₄ of the oxypropylene group are each independently an integer of 1 to 30, preferably an integer of 5 to 20, more preferably an integer of 8 to 16, More preferably an integer of 14 to 14. The total number of these repeating numbers is preferably 20 or less, more preferably 16 or less, and even more preferably 14 or less, in view of an improvement in resolution and a reduction in sludge.

As the compound represented by the above formula (5), a vinyl compound (trade name: FA-023M manufactured by Hitachi Kasei Kogyo Co., Ltd.) having R = methyl group, m ₁ + m ₂ = 6 (average value) and n ₁ = ) And the like. As the compound represented by the above formula (6), R = methyl group, m ₃ = 6 (average _{value), n 2 + n 3 =} 12 ( average value) of the vinyl compound (manufactured by Hitachi Chemical Industries whether or sikki, trade name: FA-024M ) And the like. As the compound represented by the above formula (7), a vinyl compound ( _{trade name} : NK ester HEMA ( _{trade name} , manufactured by Shin Nakamura Chemical Co., Ltd.) having R = hydrogen atom, m ₄ = 1 (average value) and n ₄ = -9P).

(B3): a compound having one ethylenic unsaturated bond in the molecule

The component (B3) is not particularly limited, but it preferably contains a compound represented by the following formula (8) in view of excellent resolution.

Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents any one of a hydrogen atom, a methyl group and a halogenated methyl group, and R ⁵ represents any one of an alkyl group having 1 to 6 carbon atoms, a halogen atom and a hydroxyl group And p represents an integer of 0 to 4. When p is 2 or more, plural R ^{5 s} present may be the same or different. - (OA) - represents an oxyethylene group and / or an oxypropylene group, and the repeating total number a of - (OA) - represents an integer of 1 to 4;

Examples of the compound represented by the formula (8) include? -Chloro? -Hydroxypropyl-? '- (meth) acryloyloxyethyl-ophthalate,? -Hydroxyethyl-?' - (Meth) acryloyloxyethyl-o-phthalate, and? -Hydroxypropyl-? '- (meth) acryloyloxyethyl-ophthalate. Among these,? -Chloro-? -β '- (meth) acryloyloxyethyl-o-phthalate is preferable. ? -chloro -? - hydroxypropyl -? '- methacryloyloxyethyl-ophthalate is commercially available as FA-MECH (product name, manufactured by Hitachi Kasei Kogyo Co., Ltd.).

The component (B) may be used alone or in combination of two or more.

The content of the component (B) in the photosensitive resin composition is preferably in the range of 30 to 60 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoints of resolution, More preferably 40 to 55 parts by mass.

By the way, the crosslinking density of the cured product of the photosensitive resin composition can be adjusted mainly by a combination of the components (A) and (B). These are adjusted to adjust the elongation at 25 ° C of the sheet-shaped cured product having a width of 10 mm and a thickness of 45 μm, which is obtained by heating the photosensitive resin composition at 120 ° C. for 1 hour under air, It is possible to follow the barrier ribs at the elongation at the time of bending of the apparatus without breakage, and breakage of the barrier ribs can be sufficiently suppressed. According to the photosensitive resin composition of the present invention, even when the image display device is bent at a radius of curvature of about 5 to 15 mm, a partition wall capable of sufficiently preventing breakage can be formed.

(C): Photopolymerization initiator

The component (C) that can be used in the present invention is not particularly limited as long as it matches the light wavelength of an exposure machine to be used. Specific examples thereof include benzophenone, N, N'-tetramethyl-4,4'-diamino Benzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; Diethylanthraquinone, 2,3-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di 2-methyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethyl anthraquinone Quinones such as quinone; Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; Benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; Methoxyphenyl) -2,2-dimethoxy-2-phenylethane-1-one, 1- (4-methoxyphenyl) Methoxyphenyl) -2-methoxy-2-propoxy-2-phenylethane-1-one, 2,2-dimethoxy-1,2-diphenylethane- Benzyl ketal such as benzyl ketal (e.g., benzyl dimethyl ketal); Acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane; N-phenylglycine, N-phenylglycine derivatives; Coumarin-based compounds; 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o- (O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- , And imidazole dimers such as 5-diphenylimidazole dimer. Also, the substituents of the aryl groups of two 2,4,5-triarylimidazoles in the 2,4,5-triarylimidazole dimer may be the same and may provide symmetrical compounds, Phosphorus compounds. In addition, a thioxanthone compound and a tertiary amine compound may be combined, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid. These may be used alone or in combination of two or more.

Among them, the component (C) preferably contains a benzyl derivative such as benzyl ketal in view of excellent curing property of the resist bottom portion after curing of the photosensitive resin composition. In view of excellent curing property of the upper portion of the resist after curing of the photosensitive resin composition, It is preferable to include both a benzidine derivative such as benzyl ketal and an acridine derivative in view of the excellent curing property of the upper portion. In particular, as the film thickness of the layer made of the photosensitive resin composition becomes thicker, it becomes necessary to balance the curing property of the resist bottom portion and the curing property of the resist upper portion.

Among them, as the component (C), it is preferable to contain an acridine derivative and a benzyl derivative in order to improve the resolution and to suppress the hemming of the resist after curing, and especially 1,7-bis (9,9'- Acridinyl) heptane and 2,2-dimethoxy-1,2-diphenylethane-1-one.

The content of the component (C) in the photosensitive resin composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, from the viewpoint of excellent light sensitivity, relative to 100 parts by mass of the total amount of the components (A) Do. From the viewpoint of excellent photocurability within the photosensitive resin composition relative to 100 parts by mass of the total amount of the component (A) and the component (B), the amount is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

Among them, when 1,7-bis (9,9'-acridinyl) heptane is contained as the component (C), the content thereof is preferably within a range of from 100 parts by mass to 100 parts by mass of the total amount of the components (A) And 0.05 to 1 part by mass, more preferably 0.1 to 0.5 part by mass, from the viewpoint of excellent optical sensitivity.

When the component (C) contains 2,2-dimethoxy-1,2-diphenylethane-1-one, its content is preferably 100 parts by mass or less per 100 parts by mass of the total of the components (A) Is preferably 1 part by mass or more, more preferably 2 parts by mass or more, from the viewpoint of excellent light sensitivity and adhesion. From the viewpoint of suppressing outgassing in the heat treatment step, the amount is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

(D): a compound having an epoxy group in the molecule

Examples of the component (D) usable in the present invention include compounds having an epoxy group (oxirane ring) in the molecule.

Examples of the compound having an epoxy group in the molecule include bisphenol F type epoxy resins such as bisphenol A diglycidyl ether and bisphenol F diglycidyl ether and bisphenol S diglycidyl ether Bisphenol S type epoxy resins, nonphenol diglycidyl ethers and the like, nonylphenol type epoxy resins such as bisacylenol diglycidyl ether, and hydrogenated bisphenol A glycidyl ethers such as hydrogenated bisphenol A A type epoxy resins, dicyclopentadiene type epoxy resins, cresol novolak type epoxy resins, and their dibasic acid modified diglycidyl ether type epoxy resins.

As these compounds, commercially available products can be used. Examples of the bisphenol A diglycidyl ether include Epikote 828, Epikote 1001 and Epikote 1002 (trade name, all manufactured by Japan Epoxy Resin Co., Ltd.) and Epikleon 1055 (trade name, manufactured by DIC Corporation) .

Examples of bisphenol F diglycidyl ether include Epikote 807 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) and bisphenol S diglycidyl ether include EBPS-200 (manufactured by Nippon Kayaku Co., Epiclon EXA-1514 (trade name, manufactured by DIC Corporation), and the like.

As the biphenol diglycidyl ether, YL-6121 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) and the like can be mentioned. As the bicalcylenol diglycidyl ether, YX-4000 (manufactured by Japan Epoxy Resin Co., Ltd.) , Trade name).

Examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (both trade names, manufactured by Tokto Kasei Kabushiki Kaisha), and Epiclon HP-7200L (DIC Epiclon N-665-EXP, Epiclon N-670-EXP-S (trade name, manufactured by DIC Corporation) can be used as the cresol novolak type epoxy resin have. Examples of the above dibasic acid-modified diglycidyl ether type epoxy resin include ST-5100 and ST-5080 (trade names, all manufactured by TOKYO KASEI KABUSHIKI CO., LTD.).

Of these, dicyclopentadiene type epoxy resins and cresol novolak type epoxy resins are preferable from the standpoint of suppressing dissolution of electrodes, and cresol novolak type epoxy resins are more preferable. The component (D) may be used alone or in combination of two or more.

The content of the component (D) in the photosensitive resin composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and more preferably 5 parts by mass or less, from the viewpoint of suppressing dissolution of the electrode, relative to 100 parts by mass of the total amount of the components (A) Or more. From the viewpoint of excellent film formability, the photosensitive resin composition is preferably 30 parts by mass or less, more preferably 20 parts by mass or less.

Component (E): Inorganic black pigment

Examples of the component (E) that can be used in the present invention include titanium black, carbon black and cobalt black, and titanium black is preferable in view of good light transmittance at wavelengths of 360 nm and 405 nm.

The content of the component (E) in the photosensitive resin composition is preferably 0.1 part by mass or more, more preferably 0.2 parts by mass or more, from the viewpoint of excellent light shielding property, relative to the total amount of 100 parts by mass of the components (A) desirable. From the viewpoint of excellent adhesion and resolution, 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable.

The photosensitive resin composition containing the above components may further contain, if necessary, a dye such as malachite green, a light coloring agent such as tribromophenylsulfone or leuco crystal violet, a plasticizer such as an anti-coloring agent, a p-toluenesulfonamide, (A) and the component (B) in a total amount of 100 parts by mass based on 100 parts by mass of the total of the components (A) and (B), other than black, a filler, defoaming agent, flame retardant, stabilizer, adhesion imparting agent, leveling agent, release promoter, antioxidant, To about 20 parts by mass, respectively. These may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention containing the above components can be obtained, for example, by homogeneously kneading and mixing the contained components with a roll mill, a bead mill or the like. If necessary, it may be dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or a mixed solvent thereof , And can be used as a solution having a solid content of about 30 to 60 mass%.

The method of forming the photosensitive resin composition layer on the substrate for an image display using the obtained photosensitive resin composition is not particularly limited, but a method of coating the photosensitive resin composition on the substrate as a liquid resist and drying can be used. In addition, a protective film may be coated on the photosensitive resin composition layer as necessary. Further, although it will be described later in detail, it is preferable to use the photosensitive resin composition layer in the form of a photosensitive element. As the protective film in the case of being used as a liquid resist and coated with a protective film after coating, there can be mentioned, for example, a polymer film such as polyethylene or polypropylene.

The photosensitive resin composition is a cured product of a sheet-shaped cured product having a width of 10 mm and a thickness of 45 占 퐉, which is obtained by heating the above photosensitive resin composition under air at 120 占 폚 for 1 hour and has an elongation at 25 占 폚 of 40% or more. The elongation percentage is preferably 40% or more, more preferably 60% or more from the viewpoint of suppressing breakage at the time of bending. The elongation percentage of the cured product can be adjusted by lowering the crosslinking density of the cured product by the combination of the component (A) and the component (B).

Here, the photo-curing of the photosensitive resin composition is carried out by exposing the photosensitive resin composition to an energy amount necessary for forming the partition wall using the photosensitive resin composition, and developing the photosensitive composition as necessary. The amount of energy is preferably such that the remaining step number after development of the 41-step tablet is 29.0.

As a concrete measurement method of the elongation percentage of the cured product, a cured product is formed into a sheet having a width of 10 mm and a thickness of 45 탆, and when the cured product is broken at a constant speed of 25 캜, a distance between chucks of 50 mm and a speed of 2 cm / The elongation percentage (%) in the case of tensile strength is obtained by the following equation.

Elongation (%) = {(length at break - initial length) / initial length} x 100

The photosensitive resin composition was prepared by forming a photosensitive resin composition layer composed of the photosensitive resin composition described above on a transparent electrode and then photo-curing the photosensitive resin composition layer. The photosensitive resin composition layer was heated at 120 ° C for 1 hour in air, RH, a DC voltage of 80 V is applied to the transparent electrode for 100 hours.

Here, the photo-curing of the photosensitive resin composition layer is carried out by exposing the photosensitive resin composition layer to an energy amount necessary for forming the partition wall by using the photosensitive resin composition layer, and developing it as necessary. The amount of energy is preferably such that the remaining step number after development of the 41-step tablet is 29.0.

As a specific method for determining the dissolution of the transparent electrode, the resistance value of the anode is measured by a tester, the measurable value is determined as no disconnection due to dissolution, and the unmeasurable value is determined as disconnection due to dissolution. Further, for the measurable value, the rate of increase from the initial resistance value may be obtained.

(Photosensitive element)

1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. 1, the photosensitive element 10 of the present invention comprises a support 1, a photosensitive resin composition layer 2 composed of the photosensitive resin composition formed thereon, and a photosensitive resin composition layer 2 formed on the photosensitive resin composition layer 2, And a protective film (3). In addition, the protective film 3 is provided if necessary.

As the support 1, for example, polymer films such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be preferably used. The thickness of the polymer film is preferably about 1 to 100 mu m, more preferably 5 to 50 mu m, and even more preferably 10 to 30 mu m. In addition, when the support 1 is transparent, it is preferable that exposure can be performed through the support 1 when the photosensitive resin composition layer 2 is exposed.

The method of forming the photosensitive resin composition layer 2 on the support 1 is not particularly limited, but can be preferably carried out by applying a solution of the photosensitive resin composition and drying the solution. The thickness of the photosensitive resin composition layer to be applied varies depending on required characteristics, but it is preferably 10 to 100 占 퐉, more preferably 20 to 100 占 퐉, more preferably 30 to 100 占 퐉 in thickness after drying , And particularly preferably from 40 to 100 탆.

The application can be carried out by a known method such as roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater and the like. The drying can be performed at, for example, 70 to 150 ° C for about 2 to 30 minutes. The amount of the residual organic solvent in the photosensitive resin composition layer (2) is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.

The protective film 3 may be laminated on the photosensitive resin composition layer 2 formed on the support 1 to cover the surface of the photosensitive resin composition layer 2. [ It is preferable that the adhesive force between the photosensitive resin composition layer 2 and the protective film 3 is smaller than the adhesive force between the photosensitive resin composition layer 2 and the support 1 as the protective film 3, An olefin-based film such as polypropylene or a polyester film typified by polyethylene terephthalate is used. In the case of using a polyester film as the support 1 and using the same kind of polyester film as the protective film 3, the protective film 3, which has been subjected to a processing treatment on the surface contacting the photosensitive resin composition layer desirable.

Further, these protective films (3) are preferably films of low fish eyes. The term "fish eye" as used herein means that a foreign substance, an undissolved product, an oxidized heat, or the like of a material is introduced into the film when the film is produced by thermally melting the material and kneading, extruding, biaxially stretching or casting. In other words, the term " low fish eye " means that the foreign substance or the like in the film is small.

The photosensitive element 10 may have an intermediate layer or a protective layer such as a cushion layer, an adhesive layer, a light absorbing layer and a gas barrier layer in addition to the photosensitive resin composition layer 2, the support 1 and the optional protective film 3 have.

The produced photosensitive element 10 is usually wound by winding on a cylindrical core. At this time, it is preferable that the support body 1 is wound to the outside. It is preferable that an end surface separator is provided on the end surface of the roll-on photosensitive element roll from the viewpoint of end surface protection, and it is desirable to provide a moisture-proof end surface separator in view of edge fusion resistance. The term "edge fusion" as used herein refers to a phenomenon in which the photosensitive resin composition layer 2 escapes from an end face, which is also referred to as a "cold flow". This phenomenon is undesirable because it becomes a foreign matter generating source at the time of forming the barrier rib. Further, as the wrapping method, it is preferable to wrap wrapped in a black sheet having a small moisture permeability and excellent light shielding property. As the material of the above-mentioned core, a plastic such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, an ABS resin (acrylonitrile-butadiene-styrene copolymer) can be mentioned.

(Method of forming partition wall of image display apparatus, method of manufacturing image display apparatus, and image display apparatus)

Next, a description will be given of a method of forming a partition wall of an image display apparatus using the photosensitive resin composition or photosensitive element of the present invention, a method of manufacturing an image display apparatus, and an image display apparatus.

2 (a), an electrode substrate 30 composed of an electrode 4 and a substrate 5 is prepared, and as shown in Fig. 2 (b), the electrode substrate 30, The photosensitive resin composition layer 2 and the support 1 in the above-described photosensitive element 10 are laminated (lamination step).

The substrate 5 constituting the electrode substrate 30 is not particularly limited as long as it is a flexible substrate, and examples thereof include an insulating substrate such as a polymer film substrate and a semiconductor substrate such as a silicon substrate. Examples of the electrode substrate 30 include a substrate 5 on which an electrode 4 having flexibility such as ITO, IZO, and Ag wire / ink is formed. Examples of the method for forming the electrode 4 include a method of forming a pattern by using a photolithography method and a method of patterning an electrode material having photosensitivity, and the like, by laminating the electrode material by vapor deposition or sputtering. The method of forming the electrode 4 is not particularly limited.

As a method of laminating the photosensitive resin composition layer 2 onto the electrode substrate 30, a method of applying the solution of the photosensitive resin composition onto the electrode substrate 30 and drying it, in addition to the above-described method using the photosensitive element 10 May be used.

When the protective film 3 is present on the photosensitive resin composition layer 2, the protective film 3 is removed and the protective film 3 is laminated on the electrode substrate 30 by using the photosensitive element 10. As the lamination condition, for example, the photosensitive resin composition layer 2 is pressed on the electrode substrate 30 at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ) while heating the photosensitive resin composition layer 2 to about 70 to 130 ° C , Or the like, and it is also possible to laminate under reduced pressure. Although the surface of the electrode substrate 30 is usually formed with an electrode pattern, it may be flat or may have unevenness if necessary.

2 (b), the photosensitive resin composition layer 2 is irradiated with an actinic ray 8 on the image side to thereby photo-cure the exposed portion (exposure step) . 2 (b), a mask pattern 7 is provided on the photosensitive resin composition layer 2 to form an active ray 8 on a screen. And the photosensitive resin composition layer 2 of the exposed portion is photo-cured. The mask pattern 7 may be a negative type or a positive type, and a commonly used mask pattern 7 may be used. As the light source of the active ray 8, a known light source, for example, a carbon arc, a mercury vapor arc, etc., a high pressure mercury lamp, a xenon lamp, and the like are used. As the exposure method, a direct imaging exposure method in which a pattern is directly drawn by a laser without using the mask pattern 7 may be used.

After the exposure, as shown in Fig. 2C, the photosensitive resin composition layer 2 of the unexposed portion is selectively removed by development to form a photo-cured product (photosensitive resin composition layer) on the substrate (the electrode substrate 30) The pattern 20 is formed (developing step). Further, in the developing step, if the support 1 exists, the support 1 is removed prior to development.

The development is carried out by removing the unexposed portion by wet development with a developing solution such as an alkaline aqueous solution, aqueous developing solution or organic solvent, or dry development. In the present invention, an alkaline aqueous solution is preferably used. Examples of the alkaline aqueous solution include a lean solution of 0.1 to 5 mass% sodium carbonate, a lean solution of 0.1 to 5 mass% potassium carbonate, and a lean solution of 0.1 to 5 mass% potassium hydroxide. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to developability of the photosensitive resin composition layer. A surfactant, defoaming agent, organic solvent or the like may be mixed into the alkaline aqueous solution. Examples of the developing method include a dip method, a spray method, a brushing method, and a slapping method, but a spraying method is preferable for improving the resolution.

As the post-development processing, it is preferable that the formed photocrypted pattern 20 is further cured by heat treatment at about 60 to 250 캜, if necessary. The curing temperature is preferably about 80 to 200 占 폚, and more preferably about 100 to 150 占 폚. The curing time is not particularly limited, but is preferably 10 minutes to 3 hours, more preferably 30 minutes to 2 hours.

The process of filling the display medium such as particles in the photo-curable pattern 20 formed in the above step and the step of pasting the other electrode substrate 30 to the photo-curable pattern 20 (e)) and the like, and the manufacture of the image display apparatus can be completed.

The step of attaching the other electrode substrate 30 to the light guide pattern 20 can be carried out as follows. 2 (d), the adhesive 40 is laminated on the photocurable pattern 20, and the adhesive 40 is applied to the electrode 40 by the adhesive 40 as shown in FIG. 2 (e) Is performed by adhering the substrate 30 and the photopolymer pattern 20 to each other. Further, at least a transparent electrode substrate is used for the electrode substrate on the display surface side of the image display apparatus.

The image display device formed through the above-described processes includes the electrode substrate 30 having flexibility and the partition wall made of the photo-curable pattern 20 having a high elongation, so that excellent flexibility can be achieved. Particularly, depending on the selection of the material of the electrode 4, an image display device having a high degree of bendability that can cope with a radius of curvature of about 5 to 15 mm can be obtained. Further, even when the image display device is bent at a radius of curvature of about 5 to 15 mm, the partition wall formed using the photosensitive resin composition of the present invention can sufficiently suppress the occurrence of breakage.

<Examples>

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples without departing from the technical idea of the present invention.

(Examples 1 to 4 and Comparative Examples 1 to 5)

The components (A), (B), (C), (E) and other components shown in Table 1 were mixed and then added with the component (D) 4 and Comparative Examples 1 to 5 were obtained. The blending amount (unit: g) of each component is as shown in Table 1.

Details of each component in Table 1 are as follows. With respect to the component (A), the following amounts were mixed as the resin solution, but the amount of the solid content was shown in Table 1.

(A) Component: Binder polymer

*One; 48 mass% methyl cellosolve / toluene (weight ratio 6/4) of methacrylic acid / methyl methacrylate / butyl methacrylate copolymer (resin A, mass ratio 30/35/35, weight average molecular weight 50000, acid value 196) 93.75 g of a solution (solid content 45 g)

*2; Methyl methacrylate / methyl methacrylate / benzyl methacrylate / styrene copolymer (resin B, mass ratio 30/5/25/40, weight average molecular weight 56,000, acid value 196) methylcellosolve / toluene (mass ratio 6/4) solution 93.75 g (solid content 45 g)

(B) Component: Photopolymerizable compound

* 3; (Weight average molecular weight: 4,000, trade name: HT-9082-95, manufactured by Hitachi Kasei Kogyo Co., Ltd.) obtained by reacting a polycarbonate compound having a terminal hydroxyl group, an organic isocyanate and 2-hydroxyethyl acrylate,

*4; UA-21EB (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)

* 5; FA-023M (trade name, manufactured by Hitachi Kasei Kogyo Co., Ltd.)

* 6; FA-024M (trade name, manufactured by Hitachi Kasei Kogyo Co., Ltd.)

* 7; ? -chloro-? -hydroxypropyl-? '- methacryloyloxyethyl-ophthalate (trade name: FA-MECH, manufactured by Hitachi Kasei Kogyo Co., Ltd.)

(C): Photopolymerization initiator

*8; N, N'-tetraethyl-4,4'-diaminobenzophenone (trade name: EAB, manufactured by Hodogaya Chemical Co., Ltd.)

* 9; Tribromomethylphenyl sulfone (product name: TPS, manufactured by Sumitomo Seika Chemical Co., Ltd.)

* 10; 17-bis (9-acridinyl) heptane (trade name: N-1717, manufactured by Adeka Corporation)

* 11; Benzyl dimethyl ketal (trade name: I-651, manufactured by Ciba Specialty Chemicals K.K.)

(D): a compound having an epoxy group in the molecule

* 12; Cresol novolak type epoxy resin (trade name: EPICLON N-670-EXP-S, manufactured by DIC Corporation)

* 13; Dicyclopentadiene type epoxy resin (trade name: Epiclon HP-7200L, manufactured by DIC Kabushiki Kaisha)

* 14; Bisphenol A type epoxy resin (trade name: Epiclon 1055, manufactured by DIC Kabushiki Kaisha)

* 15; Cresol novolak type epoxy resin (trade name: Epiclon N-665-EXP, manufactured by DIC Corporation)

The block isocyanate compound

* 16; Block isocyanate (Sumitomo Bayer Urethane Co., Ltd., trade name: Sumidur BL3175)

* 17; Block isocyanate (trade name: Desmodur BL3475, manufactured by Sumitomo Bayer Urethane Co., Ltd.)

* 18; Block isocyanate (trade name: Desmodur VPLS2253, manufactured by Sumitomo Bayer Urethane Co., Ltd.)

Component (E): Inorganic black pigment

* 19; A titanium black dispersion (trade name: BT-1HCA, manufactured by Gemco)

Other ingredients

* 20; A pigment dispersant (trade name: Florene DOPA-17HF, manufactured by Kyoeisha Chemical Co., Ltd.)

* 21; Methacryloyloxypropyltrimethoxysilane (trade name: SZ-6030, manufactured by Dow Corning Toray Industries, Inc.)

Next, the obtained solution of the photosensitive resin composition was uniformly coated on a polyethylene terephthalate film (trade name: HTR-02, manufactured by Daikin DuPont Film Co., Ltd.) having a thickness of 16 탆 and dried in a hot air convection dryer at 90 캜 And dried for 10 minutes to form a photosensitive resin composition layer. Thereafter, the photosensitive resin composition layer was protected with a polyethylene protective film (tensile strength in the longitudinal direction of the film: 16 MPa, tensile strength in the film width direction: 12 MPa, trade name: NF-15, manufactured by Tama Polyurethane K.K.) Element. The thickness of the photosensitive resin composition layer after drying was 45 占 퐉.

The photosensitive element was peeled off on the ITO side of the ITO-attached PET substrate (trade name: R-300, manufactured by Toyo Boseki Co., Ltd.) so that the photosensitive resin composition layer was in contact with the ITO-coated PET substrate surface And then passed through a laminate roll heated to 110 DEG C to laminate. The structure of the obtained laminate is a PET substrate with ITO, a photosensitive resin composition layer, and a polyethylene terephthalate film from the bottom. The resulting laminate was evaluated for sensitivity, adhesion, resolution, and seam folding.

&Lt; Evaluation of sensitivity &

Using a parallel light exposure machine EXM-1201 (Oak Seisakusho Kabushiki Kaisha) having a high-pressure mercury lamp, a phototool having a 41-step tablet was brought into close contact with the polyethylene terephthalate film of the laminate to perform exposure. After the exposure, the polyethylene terephthalate film was peeled off, and a 1 mass% sodium carbonate aqueous solution was sprayed at 30 캜 for 20 seconds to remove unexposed portions of the photosensitive resin composition layer. The energy amount (exposure amount) at which the step number of steps of the 41 stepped tablet after development became 29.0 was defined as sensitivity (mJ / cm ² ). The smaller the value of the energy amount, the higher the sensitivity. Table 2 shows the evaluation results. Table 2 shows the actual remaining number of steps when exposure was performed with the energy amount.

&Lt; Evaluation of adhesion &

A line width / space width of 10/300 to 80/300 (unit: μm) and a space width (width of 1 mm) were measured as a negative adhesion evaluation value by using a parallel light exposure machine EXM-1201 (manufactured by Oak Seisakusho KK) having a high pressure mercury lamp. And a phototool having a 41-step step tablet were brought into close contact with the polyethylene terephthalate film of the laminate, and exposure was performed with an energy amount such that the remaining step number after development of the 41-step step tablet was 29.0 . After the exposure, the polyethylene terephthalate film was peeled off, and a 1 mass% sodium carbonate aqueous solution was sprayed at 30 캜 for 20 seconds to remove the unexposed portions of the photosensitive resin composition layer to evaluate the adhesion. The adhesion is expressed by the width (μm) of the smallest line remaining without being peeled off by the developing solution. The smaller the value is, the higher the adhesion is in that it is in close contact without peeling from the glass substrate even in a thin line. Table 2 shows the evaluation results.

<Evaluation of resolution>

A phototool having a 41 step tablet and a phototool having a wiring pattern with a line width / space width of 30/30 to 200/200 (unit: μm) as a negative resolution evaluation, are placed on the polyethylene terephthalate film of the laminate , And exposure was carried out using a parallel light exposure apparatus EXM-1201 (manufactured by Oak Seisakusho Co., Ltd.) having a high-pressure mercury lamp, at an energy amount such that the remaining step number after development of the 41 step step tablet was 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and an unexposed portion of the photosensitive resin composition layer was removed by spraying a 1 mass% sodium carbonate aqueous solution at 30 캜 for 20 seconds to evaluate the resolution. The resolution is expressed by the smallest space width (μm) in which the unexposed portion is well removed by the developing process, and the smaller the value is, the better the resolution is.

Table 2 shows the evaluation results.

<Simultaneous folding test>

Using a parallel light exposure machine EXM-1201 (manufactured by Oak Seisakusho Co., Ltd.) having a high-pressure mercury lamp, exposure was performed at an energy amount such that the remaining step number after development of the 41 step step tablet was 29.0. After the exposure, the polyethylene terephthalate film was peeled off and a 1 mass% sodium carbonate aqueous solution was sprayed at 30 캜 for 20 seconds to remove unexposed portions of the photosensitive resin composition layer. Then, it was left in a box-type dryer (Mitsubishi Denki Kabushiki Kaisha, model number: NV50-CA, air atmosphere) heated to 120 占 폚 for 1 hour. The resultant evaluation sheet was subjected to a core shrinkage to obtain a film A in which the cured product of the photosensitive resin composition layer from the ITO-adhered PET substrate was not peeled and no breakage was observed, or peeled or broken from the ITO-attached PET base material.

&Lt; Solubility of electrode >

The photosensitive element was applied to the surface of the IZO-TEG substrate and the ITO-TEG substrate, respectively, on the IZO-TEG (Test Element Group) substrate and the IZO and ITO surface of the ITO- The laminate was passed through a laminate roll heated at 110 캜 while peeling the protective film made of polyethylene so as to be laminated. The structure of the obtained laminate is a TEG substrate, a photosensitive resin composition layer, and a polyethylene terephthalate film from the bottom. A photo tool having a 41-step tablet was brought into close contact with the polyethylene terephthalate film of the laminate. Using a parallel light exposure machine EXM-1201 (manufactured by Oak Seisakusho Kabushiki Kaisha) having a high-pressure mercury lamp, Was 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 1 mass% sodium carbonate aqueous solution was sprayed at 30 캜 for 20 seconds to remove unexposed portions of the photosensitive resin composition layer. Thus, an evaluation substrate on which a photo-cured product of the photosensitive resin composition layer was formed on a TEG substrate was obtained. Subsequently, the obtained evaluation substrate was placed in a box-type dryer (Mitsubishi Denki Kabushiki Kaisha, model number: NV50-CA) heated to 120 DEG C for 1 hour. Thereafter, a DC voltage of 80 V was applied to the electrodes of the evaluation substrate under the conditions of 60 DEG C and 90% RH, and the resistance value of the positive electrode after 100 hours was measured by a tester. Table 2 shows the evaluation results. In the table, A indicates that the resistance value can be measured, and it is determined that there is no disconnection due to dissolution, and B indicates that it is determined that disconnection due to dissolution is impossible. For A, the value obtained by dividing 100 times the resistance value of the positive electrode after 100 hours divided by the initial resistance value is described as a resistance increase rate (%). It can be estimated that the dissolution of the electrode is suppressed as the value of the rate of increase of the resistance is smaller.

<Elongation of cured product>

The photosensitive element was peeled off on a polytetrafluoroethylene sheet (manufactured by Nitto Denko Kagaku Co., Ltd., product name: Nitoflon film No. 900 U) while the protective film made of polyethylene was peeled off so that the photosensitive resin composition layer was in contact with the surface of the polytetrafluoroethylene sheet And then passed through a laminate roll heated to 110 DEG C to laminate. The structure of the obtained laminate is a poly (tetrafluoroethylene sheet), a photosensitive resin composition layer, and a polyethylene terephthalate film. The laminate was exposed from a polyethylene terephthalate film using a parallel light exposure machine EXM-1201 (manufactured by Oak Seisakusho Co., Ltd.). Further, in the exposure of the laminate, the energy amount was set so that the number of remaining step steps after development of the 41-step step tablet was 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 1 mass% sodium carbonate aqueous solution was sprayed at 30 캜 for 30 seconds to remove unexposed portions of the photosensitive resin composition layer. Thus, a evaluation sheet having a photo-cured product of the photosensitive resin composition layer formed on the poly (tetrafluoroethylene) sheet was obtained. Then, the obtained evaluation sheet was placed in a box-type dryer (Mitsubishi Denki Kabushiki Kaisha, model number: NV50-CA, air atmosphere) heated to 120 占 폚 for 1 hour. The evaluation sheet after the heat treatment was cut to a width of 10 mm and stretched until the cured product of the photosensitive resin composition layer was broken at a constant speed of 2 cm / min at a distance of 50 mm between the chucks, The elongation percentage (%) of water was determined. Table 2 shows the evaluation results.

As is apparent from the results shown in Table 2, it was confirmed that dissolution of the electrode was inhibited by the presence of the component (D). In addition, as for the elongation, it was confirmed that a high elongation of 40% or more can be obtained, and breakage of the barrier rib at the time of bending can be suppressed.

&Lt; Industrial applicability >

INDUSTRIAL APPLICABILITY As described above, the present invention provides a photosensitive resin composition capable of forming barrier ribs for an image display device capable of suppressing breakage at the time of bending while suppressing dissolution of electrodes when a voltage is applied under high temperature and high humidity, A photosensitive element using the same, a method of forming a partition wall of an image display apparatus, a method of manufacturing an image display apparatus, and an image display apparatus can be provided.

1: Support
2: Photosensitive resin composition layer
3: Protective film
4: Electrode
5: substrate
10: photosensitive element
20: Cured product of the photosensitive resin composition (photo-curable pattern)
30: electrode substrate
40: Adhesive

Claims (13)

A photosensitive resin composition for forming a partition for separating a pixel in an image display apparatus having bendability provided with at least a transparent electrode on a display surface,
The photosensitive resin composition
(A): a binder polymer having a carboxyl group in a molecule,
Component (B): Photopolymerizable compound,
(C) Component: a photopolymerization initiator,
(D): a compound having an epoxy group in the molecule, and
Component (E): Inorganic black pigment
&Lt; / RTI &gt;
Wherein the component (A) comprises a binder polymer comprising butyl methacrylate in its structural unit,
The component (B) comprises the component (B1): a compound having an ethylenic unsaturated group and a urethane bond in the molecule. The photosensitive resin composition according to claim 1, wherein the component (B) comprises a compound obtained by reacting a component (B2): an?,? - unsaturated carboxylic acid with a polyhydric alcohol and / or a glycidyl group-containing compound. The photosensitive resin composition according to claim 1, wherein the component (B) comprises a component (B3): a compound having one ethylenic unsaturated bond in the molecule. The photosensitive resin composition according to claim 1, wherein the component (E) comprises titanium black. A photosensitive element comprising a support and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 4 formed on the support. A method of forming a barrier rib of an image display apparatus having flexibility, comprising at least a transparent electrode arranged on a display surface, and a partition wall separating pixels,
A lamination step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 4 on a substrate of the image display apparatus;
An exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photo-cure the exposed portion,
A developing step of removing a portion of the photosensitive resin composition layer other than the exposed portion to form a photopolymerizable pattern
Of the barrier ribs of the image display apparatus. A manufacturing method of an image display device having flexibility, comprising at least a transparent electrode arranged on a display surface, and a partition wall separating pixels,
A manufacturing method of an image display device, comprising the step of forming the barrier ribs by the method according to claim 6. The manufacturing method of an image display apparatus according to claim 7, wherein the transparent electrode is made of a material formed by applying a solution containing at least one kind of metal conductive fibers. The method according to claim 7, further comprising the steps of:
A step of attaching the substrate to the opposite side of the partition wall so as to face the one substrate
The method comprising the steps of: An image display device manufactured by the manufacturing method according to claim 7. delete delete delete

Images