CN105607424A - Photosensitive resin composition, photosensitive element, method for formation of septum for image display device, image display device, process for production of image display device, and application - Google Patents

Abstract

The invention provides a photosensitive resin composition, a photosensitive element, a method for forming a partition wall, an image display device, a manufacturing method, and an application. The photosensitive resin composition is a photosensitive resin composition for forming a partition wall separating pixels in an image display device, and the image display device is a flexible image display device provided with a transparent electrode at least on a display surface , the photosensitive resin composition contains (A) component: a binder polymer having a carboxyl group in the molecule, (B) component: a photopolymerizable compound, (C) component: a photopolymerization initiator, and (D) Ingredient: A compound with an epoxy group in the molecule. After the photosensitive resin composition is photocured, it is heated at 120°C for 1 hour in the air to form a sheet-like cured product with a width of 10mm and a thickness of 45μm at 25 The elongation at °C is 40% or more.

Description

Photosensitive resin composition, photosensitive element, method for forming partition, image display device, manufacturing method, and application

The application date is June 3, 2011, the application number is 201180020927.6, and the title of the invention is "photosensitive resin composition, a photosensitive element using it, a method for forming a partition wall of an image display device, and an image display device." A divisional application of the Chinese patent application for manufacturing method and image display device.

technical field

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

Background technique

In recent years, an image display device (PLD: Paper Like Display) that is as thin as paper, can be freely carried by hand, and can display characters and images has attracted attention. This image display device has the advantages of paper as a common printed matter, that is, visibility and portability, and since information can be converted into an electronic form, it is also trying to be practical as a substitute for paper from the viewpoint of the environment and cost. change.

As display technologies for image display devices, various types such as a type that moves particles by electrophoresis, a liquid crystal type, and an electrochemical type have been devised (see, for example, Non-Patent Document 1). In particular, methods such as microcapsule electrophoresis, microcup electrophoresis, electronic powder fluid, and toner display are being studied as methods for moving particles. In these methods, white and black particles serving as a display medium are enclosed between transparent electrodes and an electric field is applied to electrically move these particles to form a white/black image for display. In addition, there are active driving and passive driving as drive methods for image display devices, and studies on backside technology (panel circuits) for image display devices are also underway.

In the case of the image display device of the particle movement type described above, a partition wall for enclosing white/black particles as described above is required. As a method for forming this partition wall, a mold transfer method, a screen printing method, a sandblasting method, a photolithography method, an additive method, and the like have been proposed (for example, refer to Patent Document 1). Among them, photolithography, which can efficiently form a high-definition pattern by irradiating an active ray using a photosensitive resin composition, has attracted attention.

Recently, there have also been studies on the flexibility of image display devices, and reports on realizing full-color display by combining color filters in white/black image display (see, for example, Non-Patent Document 2).

Flexibility of the electrode substrate is required for flexible image display devices. In the past, ITO (Indium Tin Oxide), which was used as a transparent electrode, lacked flexibility. Therefore, in recent years, research on ITO substitutes such as IZO (Indium Zinc Oxide), Ag wire ink, and organic conductive materials has been ongoing. (For example, refer to Non-Patent Document 3). Various studies have been made on the degree of flexibility ranging from the degree of being bendable to the degree of being able to be slightly rounded to reduce the volume when carried. As the radius of curvature in the case of a small round, it is generally assumed that the bendability limit of the ITO electrode substrate is about 15 to 20mm, but in the case of Ag wire ink, organic conductive material, and the combination thereof, the radius of curvature can be reduced. As small as about 5-15mm.

In addition, when performing full-color display, it is necessary to increase the contrast between pixels in order to use color filters together in an image display device for white/black display. Therefore, a light-shielding layer for blocking light between pixels is required. In the case of monochrome display, there are cases where transparency is required instead of light-shielding properties in order to improve the brightness of an image on an image display device without using a color filter.

The partition wall of the image display device using photolithography is formed as follows. That is, a method including a step of laminating a light-shielding layer called a black matrix (black matrix) on a substrate by photolithography, and further coating a photosensitive resin composition on the light-shielding layer, or laminating A step of forming a photosensitive resin composition layer for a photosensitive element, a step of irradiating a predetermined portion of the photosensitive resin composition layer with active light to photocure the exposed portion, and a step of removing an unexposed portion to form a photocured product pattern . Here, a light-shielding layer called a black matrix may also be omitted. Therefore, sensitivity, resolution, and adhesiveness to a board|substrate are generally required for the photosensitive resin composition used for forming the partition of an image display apparatus.

In addition, in the case of manufacturing an image display device, it further includes a step of filling a display medium such as particles into the photocured pattern obtained in the above steps, a step of heat-treating the photocured pattern, and a step of attaching an electrode substrate. Thereby, the image display apparatus which made the hardened|cured material of the photosensitive resin composition layer into partition walls can be obtained.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2007-178881

non-patent literature

Non-Patent Document 1: Akira Suzuki, "The Latest Trend of Electronic Paper 2007 (The Latest Trend of Electronic Paper 2007)", October 10, 2007, Journal of the Graphic Society of Japan Vol. 46 No. 5: 372-384 (2007 )

Non-Patent Document 2: Takeo Tanuma, "Flexible Electronic Paper Using Electron Powder Fluid (Electronic Powder Fluid を用いたフレキシブル电子ペーパー)", October 10, 2019, Journal of the Graphic Society of Japan Vol. 46 No. 5 : 396-400 (2007)

Non-Patent Document 3: Nezu Takeru, "Introduction of New Materials to Transparent Electrodes (Transparent Electrode に New Materials を Introduction)", August 10, 2009, Nikkei Electronics 59-65 (2009)

Contents of the invention

The problem to be solved by the invention

In the step of affixing the electrode substrate, since voltage is applied under high temperature and high humidity, there is a possibility that the electrode portion in close contact with the cured product of the photosensitive resin composition will be melted. In fact, IZO, which has been studied as a base material for a flexible counter electrode, has a problem of melting during the process of attaching the above-mentioned electrode substrate because it contains zinc, an amphoteric metal. Furthermore, electrode materials that have a high degree of bendability and can achieve a curvature radius of about 5 to 15 mm, for example, when the electrode material uses Ag wire ink, an organic conductive material, and a combination thereof, there is a possibility that the partition wall material is bent. problem of breakage.

Therefore, the present invention is made in view of the above-mentioned problems, and its object is to provide a photosensitive resin composition capable of suppressing melting of electrodes and forming a partition wall capable of suppressing breakage during bending, and a photosensitive element using the photosensitive resin composition for image display. A method of forming a partition wall of a device, a method of manufacturing an image display device, and an image display device.

solutions to problems

In order to achieve the above object, the present invention provides a photosensitive resin composition, which is a photosensitive resin composition used to form a partition wall separating pixels in an image display device, the image display device is equipped with A flexible image display device having a transparent electrode, wherein the photosensitive resin composition contains (A) component: a binder polymer having a carboxyl group in the molecule, (B) component: a photopolymerizable compound, and (C) component : A photopolymerization initiator, and (D) component: The compound which has an epoxy group in a molecule|numerator, after photocuring the said photosensitive resin composition, and heating at 120 degreeC for 1 hour in air, the width 10mm, thickness The elongation at 25° C. of the 45 μm sheet-shaped cured product is 40% or more.

According to the photosensitive resin composition which has the said structure, melting of the electrode which becomes a problem when forming the partition of an image display apparatus can be suppressed, and the partition which can suppress the breakage at the time of bending can be formed. Moreover, according to the said photosensitive resin composition, the photocured material pattern excellent in resolution and adhesiveness can be formed with good sensitivity. The detailed reason why the melting of the electrode is suppressed by the photosensitive resin composition of the above-mentioned structure is not clear, but it is considered that the above-mentioned (D) component captures the carboxyl group remaining in the cured product of the photosensitive resin composition, thereby suppressing the melting of the electrode. of melting. In addition, it is considered that the reason for suppressing the breakage of the partition wall during bending is that by reducing the crosslink density of the cured product of the photosensitive resin composition and adjusting the elongation to the above-mentioned range, the partition wall can be kept in a state where the breakage does not occur. The elongation following bending of the image display device is lower. According to the photosensitive resin composition of the present invention, even when the image display device is bent with a radius of curvature of about 5 to 15 mm, it is possible to form a partition capable of sufficiently suppressing the occurrence of damage.

The photosensitive resin composition of this invention may further contain (E)component: Inorganic black pigment. Moreover, it is preferable that the said (E) component contains titanium black. Contrary characteristics such as sensitivity and light-shielding property can be maintained in a well-balanced manner by containing this (E) component. On the other hand, in order to improve the brightness of an image display device, a photosensitive resin composition for forming a partition wall and a photosensitive element using the same that does not contain the inorganic black pigment (component (E)) may be required in some cases. , therefore (E) component may be added as needed.

The present invention also provides a photosensitive element including a support, and a photosensitive resin composition layer formed on the support and comprising the above-mentioned photosensitive resin composition of the present invention. By using such a photosensitive element, it is possible to suppress melting of an electrode which is a problem when forming a partition of an image display device, and to form a partition capable of suppressing breakage during bending. Moreover, according to this photosensitive element, a photocured product pattern excellent in resolution and adhesion can be formed with good sensitivity.

The present invention further provides a method for forming a partition wall of an image display device, which is a method for forming a partition wall of an image display device having flexibility, including at least a transparent electrode disposed on a display surface and a partition wall separating pixels, The method for forming the partition wall of the image display device includes a step of laminating a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention on the substrate of the image display device. An exposure step of irradiating a predetermined portion of the resin composition layer with active light to photocure the exposed portion, and a development step of removing a portion of the photosensitive resin composition layer other than the exposed portion to form a pattern of a photocured product.

The present invention further provides a method for manufacturing an image display device, which is a method for manufacturing a flexible image display device provided with at least a transparent electrode disposed on a display surface and a partition wall separating pixels. The manufacturing method has the process of forming the said partition wall by the said method of forming the partition wall of the image display apparatus of this invention.

According to the above-mentioned method for forming a partition wall of an image display device and the method for manufacturing an image display device, since the partition wall is formed by the above-mentioned photosensitive resin composition of the present invention, melting of the electrodes when forming the partition wall can be suppressed, and at the same time A partition wall capable of suppressing breakage during bending can be formed.

In the above method of manufacturing an image display device, it is preferable that the transparent electrode is formed of a material obtained by applying a solution containing at least one type of metal conductive fiber. Thereby, an image display device having excellent bendability capable of realizing a radius of curvature of about 5 to 15 mm can be formed. Here, examples of the electrode material include Ag wire ink and the like.

In addition, the method for manufacturing an image display device preferably further includes a step of filling the partition wall with a display medium, and a step of attaching a substrate on the opposite side of the partition wall so as to face one of the substrates.

The present invention further provides an image display device manufactured by the above-mentioned manufacturing method. Since these image display devices are manufactured by the above-mentioned manufacturing method, they are equipped with partition walls that can suppress melting of the transparent electrodes and suppress breakage during bending, and thus have high reliability as devices.

The effect of the invention

According to the present invention, it is possible to provide a photosensitive resin composition capable of suppressing melting of an electrode when a voltage is applied under high temperature and high humidity and capable of forming a partition wall for an image display device capable of suppressing damage during bending, and a photosensitive resin composition using the same. A permanent element, a method of forming a partition wall of an image display device, a method of manufacturing an image display device, and an image display device.

Description of drawings

FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention.

FIG. 2 is a schematic cross-sectional view illustrating one embodiment of a method for forming a partition wall of an image display device using the photosensitive element of the present invention.

detailed description

Hereinafter, preferred embodiments of the present invention will be described in detail while referring to the drawings as the case may be. Here, in the drawings, the same or corresponding parts are assigned the same symbols and repeated explanations are omitted. In addition, the dimensional ratios of the drawings are not limited to the illustrated ratios. In addition, (meth)acrylic acid in this specification means acrylic acid and its corresponding methacrylic acid, (meth)acrylate means acrylate and its corresponding methacrylate, and (meth)acryloyl means acrylic acid. Acyl and its corresponding methacryloyl.

(Photosensitive resin composition)

The photosensitive resin composition of the present invention is characterized in that it is a photosensitive resin composition used for forming a partition wall separating pixels in an image display device provided with a transparent electrode at least on a display surface. A flexible image display device, wherein the photosensitive resin composition contains (A) component: a binder polymer having a carboxyl group in the molecule, (B) component: a photopolymerizable compound, (C) component: a photopolymerizable Initiator, and (D) component: a compound having an epoxy group in the molecule, a sheet with a width of 10 mm and a thickness of 45 μm obtained by photocuring the above-mentioned photosensitive resin composition and heating at 120° C. for 1 hour in air The material-like cured product has an elongation of 40% or more at 25°C.

Hereinafter, each component which can be used for the photosensitive resin composition of this invention is demonstrated in detail.

(A) Component: Binder polymer having a carboxyl group in the 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. Examples include acrylic resins, styrene resins, epoxy resins, and amide resins. Resin, amide epoxy resin, alkyd resin, phenolic resin, urethane resin. Among these, acrylic resins are preferable from the viewpoint of alkali developability. These can be used individually or in combination of 2 or more types. Examples of combinations of two or more binder polymers include two or more binder polymers composed of different copolymer components, two or more binder polymers with different weight-average molecular weights, dispersion Two or more binder polymers with different degrees. In addition, a polymer having a multimode molecular weight distribution described in JP-A-11-327137 can also be used. Here, the binder polymer may have a photosensitive group as needed.

(A) Component can be manufactured by radically polymerizing the polymerizable monomer which has a carboxyl group, and another polymerizable monomer, for example. Examples of polymerizable monomers include styrene, polymerizable styrene derivatives such as vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene, acrylamide, acrylonitrile, Esters of vinyl alcohol such as vinyl-n-butyl ether, alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, (meth)acrylate Diethylaminoethyl acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (methyl) Acrylate, (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid, etc. (meth) base) acrylic monomers, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate and other maleic acid monoesters, fumaric acid, cinnamic acid, Alpha-Cyanocinnamic Acid, Itaconic Acid, Crotonic Acid, Propiolic Acid. From the viewpoint of developability and stability, (meth)acrylic acid is preferable as a polymerizable monomer having a carboxyl group. Moreover, these can be used individually as a homopolymer, or in combination of 2 or more types can be used as a copolymer.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate Amyl acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and structural isomers thereof.

As (A) component, an acrylic copolymer containing methacrylic acid, methyl methacrylate, and butyl methacrylate is preferable from the viewpoint of being excellent in developability 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 from the viewpoint of excellent resolution. From the viewpoint of excellent developer resistance and adhesiveness, it is preferably 250 mgKOH/g or less, more preferably 240 mgKOH/g or less, still more preferably 230 mgKOH/g or less, particularly preferably 220 mgKOH/g or less. Here, when developing by a solvent is performed as a developing process, it is preferable to suppress the usage-amount of the polymerizable monomer which has a carboxyl group, and to prepare.

Here, the acid value can be measured by the following operation. That is, first, about 1 g of the solution of the resin whose acid value is to be measured was accurately weighed, and then 30 g of acetone was added to the resin solution to dissolve it uniformly. Next, an appropriate amount of phenolphthalein as an indicator was added to this solution, and titration was performed using a 0.1 N KOH aqueous solution. Then, the acid value was calculated by the following formula.

A=10×Vf×56.1/(Wp×I)

In the formula, A represents the acid value (mgKOH/g), Vf represents the titration (mL) of the KOH aqueous solution of 0.1N, Wp represents the quality (g) of the resin solution obtained by measuring, and I represents the amount (mL) of the resin solution obtained by measuring. Ratio (mass %) of volatile components.

(A) The weight-average molecular weight (measured by gel permeation chromatography (GPC) and converted from a calibration curve using standard polystyrene) of component (A) is preferably 20,000 or more, more preferably 20,000 or more from the viewpoint of excellent developing solution resistance. 25,000 or more, more preferably 30,000 or more. From the viewpoint that the developing time can be shortened, it is preferably 300,000 or less, more preferably 150,000 or less, and still more preferably 100,000 or less. Here, the weight-average molecular weight of the binder polymer is measured by gel permeation chromatography, and converted using a standard polystyrene calibration curve. The measurement conditions of gel permeation chromatography (GPC) are as follows.

[GPC measurement conditions]

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

Column: GelpackGL-R420+GelpackGL-R430+GelpackGL-R440 (3 in total) (above, manufactured by Hitachi Chemical Industries, Ltd., brand name)

Eluent: tetrahydrofuran

Measuring temperature: 25°C

Flow rate: 2.05mL/min

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

From the viewpoint of excellent coating properties of the photosensitive resin composition, the content of the component (A) in the photosensitive resin composition is preferably 40 parts by mass relative to 100 parts by mass of the total amount of the components (A) and (B) or more, and more preferably 45 parts by mass or more. From the viewpoint of excellent mechanical strength of the photocured product, 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 (A) component and (B) component.

(B) Component: Photopolymerizable compound

The (B) component that can be used in the present invention is not particularly limited as long as it can be photocrosslinked, and examples include (B1) component: a compound having an ethylenically unsaturated group and a urethane bond in the molecule, ( B2) component: a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol and/or a glycidyl group-containing compound, (B3) component: a compound having one ethylenically unsaturated bond in a molecule.

(B1) Component: A compound having an ethylenically unsaturated group and a urethane bond in the molecule

It is preferable to contain the component (B1) from the viewpoint that the elongation of the cured product can be increased and the adhesiveness to the flexible substrate is excellent.

Although it does not specifically limit as (B1) component which can be used in this invention, It is preferable to contain the compound which has an isocyanuric acid ring structure. As a compound which has an isocyanuric acid ring structure, the compound represented by following General formula (1) is mentioned, for example.

[chemical formula 1]

[In formula (1), R ¹ each independently represent a group represented by the following general formula (2), a group represented by the following general formula (3), or a group represented by the following general formula (4) As for the groups, at least one of R ¹ is a group represented by the following general formula (4). ]

[chemical formula 2]

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

[chemical formula 3]

[In formula (3), m is an integer of 1-15. ]

[chemical formula 4]

[In formula (4), 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 viewpoint of elastic modulus and adhesiveness, it is more preferable that at least two of the R in the general formula ( ¹ ) are represented by the general formula (4), and it is more preferable that all of the R are represented by the general formula ( ⁴ ). ) group represented.

In the general formulas (2), (3), and (4), m is preferably an integer of 1 to 6 from the viewpoint of being excellent in chemical resistance. Moreover, in General formula (4), it is preferable that m is an integer of 3-6 from a viewpoint of being excellent in mechanical strength.

As a commercial product of the compound represented by the above-mentioned general formula (1), for example, NKOLIGOUA-21EB (New Nakamura Chemical Industry Co., Ltd., trade name, R in the general formula ( ¹ ) All are compounds of the general formula (4) ).

In addition, the component (B1) preferably contains a compound obtained by condensation reaction of a urethane compound having a polycarbonate-derived The compound and/or the urethane bond of the reaction of the terminal hydroxyl group of a polyester compound and the isocyanate group of a diisocyanate compound, and has an isocyanate group at a plurality of terminals.

As these compounds, those synthesized by conventional methods can also be used, and commercially available ones can also be used. Commercially available products include, for example, UF-8003M, UF-TCB-50, UF-TC4-55 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), HT9082-95 (trade name, manufactured by Hitachi Chemical Industries, Ltd. ).

Furthermore, examples of (B1) components other than the above include (meth)acrylic monomers having a hydroxyl group at the β position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene Addition reactants of diisocyanate and diisocyanate compounds such as 1,6-hexamethylene diisocyanate, EO modified urethane di(meth)acrylate, EO, PO modified urethane di( meth)acrylate. As EO modified urethane di(meth)acrylate, the product name UA-11 by the Shin-Nakamura Chemical Industry Co., Ltd. is mentioned, for example. Moreover, as EO, PO modified urethane di(meth)acrylate, the product name UA-13 by the Shin-Nakamura Chemical Industry Co., Ltd. is mentioned, for example.

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

As (B2) component, for example, polyethylene glycol di(meth)acrylate (the number of ethylene groups is 2 to 14), polypropylene glycol di(meth)acrylate (the number of propylene groups is 2 to 14), 14) Etc. polyalkylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxylate trimethylolpropane (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate , Tetramethylolmethane (meth)acrylate compounds such as tetramethylolmethane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other dipentaerythritol ( Meth)acrylate compounds, bisphenol A vinyl oxide di(meth)acrylate, bisphenol A trioxyethylene di(meth)acrylate, bisphenol A decaethylene oxide di(meth)acrylate Esters such as bisphenol A vinyl dioxide di(meth)acrylate, trimethylolpropane triglycidyl ether triacrylate and bisphenol A diglycidyl ether acrylate.

Among them, from the viewpoint of making the resolution and adhesion excellent while maintaining low elasticity of the cured film, it is preferable to contain polyalkylene glycol di(meth)acrylate as the component (B2), and it is more preferable to contain polyalkylene glycol di(meth)acrylate composed of the following: A compound represented by general formula (5), (6) or (7).

[chemical formula 5]

In the above general formula (5), (6) or (7), R each independently represents a hydrogen atom or a methyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group. m ₁ , m ₂ , m ₃ and m ₄ represent the repeating numbers of structural units formed of oxyethylene groups, n ₁ , n ₂ , n ₃ and n ₄ represent the repeating numbers of structural units formed of oxypropylene groups, and ethylene oxide The total number of repetitions of the group m ₁ +m ₂ , m ₃ and m ₄ each independently represent an integer of 1 to 30, and the total number of repetitions of the oxypropylene group n ₁ , n ₂ +n ₃ and n ₄ each independently represent an integer of 1 to 30 integer.

In the compound represented by the above general formula (5), (6) or (7), the total number of repetitions m ₁ +m ₂ , m ₃ and m ₄ of the oxyethylene group is each independently an integer of 1 to 30, preferably 1 An integer of -10 is more preferably an integer of 4-9, still more preferably an integer of 5-8. The total number of repetitions is preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less from the viewpoint of excellent resolution and adhesiveness.

In addition, the total number of repetitions n ₁ , n ₂ +n ₃ and n ₄ of the oxypropylene group is each independently an integer of 1 to 30, preferably an integer of 5 to 20, more preferably an integer of 8 to 16, and still more preferably 10. An integer of ~14. The total number of repetitions is preferably 20 or less, more preferably 16 or less, and still more preferably 14 or less, from the viewpoint of excellent resolution improvement and sludge reduction.

Examples of the compound represented by the above general formula (5) include vinyl compounds (manufactured by Hitachi Chemical Industries, Ltd.) in which R=methyl, m ₁ +m ₂ =6 (average value), and n ₁ =12 (average value). , trade name: FA-023M) etc. Examples of the compound represented by the above general formula (6) include vinyl compounds (manufactured by Hitachi Chemical Industries, Ltd.) in which R=methyl, m ₃ =6 (average value), and n ₂ +n ₃ =12 (average value). , trade name: FA-024M) etc. Examples of the compound represented by the above-mentioned general formula (7) include vinyl compounds in which R=hydrogen atom, m ₄ =1 (average value), n ₄ =9 (average value). Sample name: NKESTERHEMA-9P) etc.

(B3) Component: A compound having one ethylenically unsaturated bond in the molecule

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

[chemical formula 6]

[In formula (8), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents any one of a hydrogen atom, a methyl group or a halomethyl group, R ⁵ represents an alkyl group with 1 to 6 carbon atoms, a halogen atom, Any of the hydroxyl groups, and p represents an integer of 0-4. Here, when p is 2 or more, a plurality of R ⁵ present may be the same or different. -(OA)- represents an oxyethylene group and/or an oxypropylene group, and the total number a of repetitions of -(OA)- represents an integer of 1-4. ]

Examples of the compound represented by the above general formula (8) include γ-chloro-β-hydroxypropyl-β′-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl β'-(meth)acryloyloxyethyl-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate , among which γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate is preferred. γ-Chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-phthalate is commercially available as FA-MECH (manufactured by Hitachi Chemical Industries, Ltd., product name).

The said (B) component can be used individually or in combination of 2 or more types.

The content of the component (B) in the photosensitive resin composition is preferably 30 to 60 parts by mass relative to 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoint of resolution, adhesiveness, and film formability. The range of parts by mass is more preferably 40 to 55 parts by mass.

However, the crosslinking density of the hardened|cured material of a photosensitive resin composition can be adjusted mainly by the combination of said (A) component and (B) component. By adjusting them, after photocuring the photosensitive resin composition, the elongation at 25° C. of a sheet-like cured product having a width of 10 mm and a thickness of 45 μm, which was heated at 120° C. for 1 hour in the air, was adjusted to 40% or more, the partition wall can follow the elongation when the image display device is bent without being damaged, and the damage of the partition wall can be sufficiently suppressed. According to the photosensitive resin composition of the present invention, even when the image display device is bent with a curvature radius of about 5 to 15 mm, it is possible to form a partition capable of sufficiently suppressing the occurrence of damage.

(C) Component: Photopolymerization Initiator

Component (C) that can be used in the present invention is not particularly limited as long as it is a photopolymerization initiator suitable for the light wavelength of the exposure machine used, and specific examples include benzophenone, N,N'-tetramethyl Base-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-di Methylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-methyl-1-[4-(methylthio Base) phenyl]-2-morpholino-1-propanone and other aromatic ketones, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzo Anthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9 ,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone and other quinones, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and other quinones Benzoin compounds such as benzoin, methylbenzoin, ethylbenzoin and other benzoin compounds, 1-(4-methoxyphenyl)-2,2-dimethoxy-2-phenyl Ethan-1-one, 1-(4-methoxyphenyl)-2-methoxy-2-ethoxy-2-phenylethan-1-one, 1-(4-methoxy Phenyl)-2-methoxy-2-propoxy-2-phenylethan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one ( Benzil derivatives such as benzil ketal) and other benzil derivatives, 9-phenylacridine, 1,7-bis(9,9'-acridyl)heptane and other acridine Derivatives, N-phenylglycine, N-phenylglycine derivatives, coumarin compounds, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorobenzene base)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl )-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer and other imidazole dimers. In addition, in the 2,4,5-triaryl imidazole dimer, the substituents of the aryl groups of the two 2,4,5-triaryl imidazoles may be the same to produce a symmetrical compound, or different to produce an asymmetric compound . In addition, a thioxanthone-based compound and a tertiary amine compound can also be combined like a combination of diethylthioxanthone and dimethylaminobenzoic acid. These can be used individually or in combination of 2 or more types.

Among them, as the component (C), it is preferable to contain benzil derivatives such as benzil ketal from the viewpoint of excellent curability of the resist bottom layer after curing of the photosensitive resin composition. From the viewpoint of excellent curability of the upper part of the cured resist, it is preferable to contain acridine derivatives, and it is preferable to contain benzil derivatives such as benzil ketal and acridine derivatives from the viewpoint of excellent curability of the upper and bottom parts. both. In particular, the thicker the film thickness of the layer formed of the photosensitive resin composition is, the more it is necessary to adjust the curability of the bottom portion of the resist and the curability of the upper portion of the resist in a well-balanced manner.

Among them, the component (C) preferably contains acridine derivatives and benzil derivatives, and particularly preferably contains 1,7 - Both bis(9,9'-acridyl)heptane and 2,2-dimethoxy-1,2-diphenylethan-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 from the viewpoint of excellent sensitivity with respect to 100 parts by mass of the total of the components (A) and (B) servings or more. Moreover, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of total amounts of (A) component and (B) component, and it is more preferable that it is 10 mass parts or less from a viewpoint that the photocurability inside a photosensitive resin composition is excellent. .

However, when 1,7-bis(9,9'-acridyl)heptane is contained as the above-mentioned (C) component, its content is 100 parts by mass relative to the total amount of the above-mentioned (A) component and (B) component , from the viewpoint of excellent sensitivity, it is preferably 0.05 to 1 part by mass, and more preferably 0.1 to 0.5 part by mass.

In addition, when 2,2-dimethoxy-1,2-diphenylethan-1-one is included as the above-mentioned (C) component, its content is relative to the above-mentioned (A) component and (B) component The total amount is 100 parts by mass, and from the viewpoint of excellent sensitivity and adhesiveness, it is preferably 1 part by mass or more, and more preferably 2 parts by mass or more. Moreover, from a viewpoint of suppressing outgassing in the process of a heat treatment, it is preferable that it is 10 mass parts or less, and it is more preferable that it is 5 mass parts or less.

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

As (D)component which can be used in this invention, the compound which has an epoxy group (oxiranering) in a molecule|numerator is mentioned.

Examples of compounds having an epoxy group in the molecule include bisphenol A type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F type epoxy resins such as bisphenol F diglycidyl ether, bisphenol S Bisphenol S-type epoxy resins such as diglycidyl ether, biphenol type epoxy resins such as biphenol diglycidyl ether, bixylenol type epoxy resins such as bixylenol diglycidyl ether, hydrogenated bisphenol A Hydrogenated bisphenol A type epoxy resins such as glycidyl ether, dicyclopentadiene type epoxy resins, cresol novolac type epoxy resins, and dibasic acid-modified diglycidyl ether type epoxy resins thereof.

Commercial items can be used as these compounds. For example, as bisphenol A diglycidyl ether, Epikote 828, Epikote 1001, and Epikote 1002 (all are manufactured by Japan Epoxy Resins Co., Ltd., brand name), and Epiclon 1055 (made by DIC Corporation, brand name) are mentioned.

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

In addition, examples of biphenol diglycidyl ether include YL-6121 (manufactured by Japan Epoxy Resins Co., Ltd., trade name), and examples of bixylenol diglycidyl ether include YX-4000 (Japan Epoxy Resins Co., Ltd. . System, trade name), etc.

Furthermore, examples of hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (both manufactured by Tohto Chemical Co., Ltd., trade names), and the like, and examples of dicyclopentadiene-type epoxy resins include EPICLONN-665-EXP, EPICLONN-670-EXP-S (manufactured by DIC Corporation, brand name) etc. are mentioned as cresol novolak type epoxy resin, such as EPICLONN HP-7200L (manufactured by DIC Corporation, brand name) . Moreover, ST-5100 and ST-5080 (both are manufactured by Tohto Kasei Co., Ltd., brand name) etc. are mentioned as said dibasic acid modified diglycidyl ether type epoxy resin.

Among them, dicyclopentadiene-type epoxy resins and cresol novolak-type epoxy resins are preferable from the viewpoint of suppressing melting of electrodes, and cresol novolak-type epoxy resins are more preferable. Moreover, said (D)component can be used individually or in combination of 2 or more types.

The content of the component (D) in the photosensitive resin composition is preferably 5 parts by mass or more from the viewpoint of suppressing melting of the electrode, more preferably More than 10 parts by mass. Moreover, from a viewpoint that the film-forming property of a photosensitive resin composition is excellent, it is preferable that it is 30 mass parts or less, and it is more preferable that it is 20 mass parts or less.

(E) Component: Inorganic black pigment

As (E) component which can be used in this invention, titanium black, carbon black, and cobalt black are mentioned, for example, Titanium black is preferable from a viewpoint of the light transmittance of wavelength 360nm and 405nm being favorable.

The content of the component (E) in the photosensitive resin composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass from the viewpoint of excellent light-shielding properties with respect to 100 parts by mass of the total amount of the components (A) and (B) servings or more. In addition, from the viewpoint of excellent adhesion and resolution, it is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

Regarding the photosensitive resin composition containing the above-mentioned components, dyes such as malachite green, photochromic agents such as tribromophenylsulfone and leuco crystal violet, thermal color development inhibitors, p-toluenesulfonamide, etc. can be further added as needed. Plasticizers, pigments other than black, fillers, defoamers, flame retardants, stabilizers, adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. , About 0.01-20 mass parts are contained with respect to 100 mass parts of total amounts of (A) component and (B) component, respectively. These can be used individually or in combination of 2 or more types.

The photosensitive resin composition of this invention containing the above components can be obtained by kneading and mixing a contained component uniformly, for example with a roll mill, a bead mill, etc. In addition, if necessary, dissolve in solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, or their mixed solvents , so that it can be used as a solution with a solid content of about 30 to 60% by mass.

The method of forming a photosensitive resin composition layer on a substrate for an image display device using the obtained photosensitive resin composition is not particularly limited, and a method of coating the photosensitive resin composition as a liquid resist on the above-mentioned substrate can be used. drying method. Moreover, a protective film may be coat|covered on the photosensitive resin composition layer as needed. Furthermore, as described in detail later, it is preferable to use the photosensitive resin composition layer in the form of a photosensitive element. When it is used as a liquid resist and coated with a protective film after coating, for example, a polymer film such as polyethylene or polypropylene is used as the protective film.

Regarding the photosensitive resin composition, elongation at 25°C of a sheet-shaped cured product having a width of 10 mm and a thickness of 45 μm obtained by photocuring the photosensitive resin composition and then heating the photosensitive resin composition at 120°C for 1 hour For more than 40%. From the viewpoint of suppressing breakage during bending, the elongation is 40% or more, more preferably 60% or more. The elongation of the cured product can be adjusted by reducing the crosslink density of the cured product based on the combination of (A) component and (B) component.

Here, the photocuring of the photosensitive resin composition can be implemented by exposing with the quantity of energy required when forming a partition using this photosensitive resin composition, and developing as needed. It is preferable that the quantity of the said energy is the quantity of energy which the number of remaining frames after image development of 41 exposure scales becomes 29.0.

The specific measurement method of the elongation of the cured product can use the following method, that is, the cured product is formed into a sheet shape with a width of 10 mm and a thickness of 45 μm, and the temperature is 25 ° C, the distance between the chucks is 50 mm, and the speed is 2 cm/min. The elongation (%) in the case of stretching at a constant speed until the cured product breaks is obtained by the following formula.

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

In addition, with regard to the photosensitive resin composition, it is preferable to form a photosensitive resin composition layer formed of the photosensitive resin composition on the transparent electrode, and to light-cure the photosensitive resin composition layer, and to place the photosensitive resin composition layer in air under air. Heating at 120° C. for 1 hour, and applying a DC voltage of 80 V to the transparent electrode for 100 hours under the conditions of 60° C. and 90% RH did not cause disconnection.

Here, the photocuring of the photosensitive resin composition layer can be implemented by exposing with the amount of energy required when forming a partition using this photosensitive resin composition layer, and developing as needed. It is preferable that the quantity of the said energy is the quantity of energy which the number of remaining frames after image development of 41 exposure scales becomes 29.0.

As a specific method of judging the melting of the transparent electrode, the resistance value of the anode is measured with a tester, and if it can be measured, it is judged that there is no disconnection due to melting, and if it cannot be measured, it is judged that there is a disconnection due to melting. In addition, when it is measurable, the improvement rate from an initial resistance value can also be calculated|required.

(photosensitive element)

FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. As shown in FIG. 1 , the photosensitive element 10 of the present invention includes a support 1 , a photosensitive resin composition layer 2 formed of the above photosensitive resin composition formed thereon, and a photosensitive resin composition layer 2 formed on the photosensitive resin composition layer 2 . Protective film3. Here, the protective film 3 is provided as necessary.

As the support body 1, for example, a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, polyester, or the like can be preferably used. The thickness of the polymer film is preferably about 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 10 to 30 μm. Moreover, when the support body 1 is transparent, when performing exposure to the photosensitive resin composition layer 2, since exposure can be performed through the support body 1, it is preferable.

The formation method of forming the photosensitive resin composition layer 2 on the support body 1 is not specifically limited, It can implement preferably by applying and drying the solution of the photosensitive resin composition. The thickness of the applied photosensitive resin composition layer varies depending on the required properties, but the thickness after drying is preferably about 10 to 100 μm, more preferably 20 to 100 μm, still more preferably 30 to 100 μm, particularly preferably 40～100μm.

Coating can be performed by known methods such as roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater, and the like, for example. Drying can be performed, for example, at 70 to 150° C. for about 2 to 30 minutes. Moreover, it is preferable that the residual organic solvent amount in the photosensitive resin composition layer 2 is 2 mass % or less from a viewpoint of preventing the percolation of an organic solvent in a subsequent process.

The surface of the photosensitive resin composition layer 2 can also be covered by laminating the protective film 3 on the photosensitive resin composition layer 2 formed on the support body 1. As the protective film 3, compared with the adhesive force between the photosensitive resin composition layer 2 and the support body 1, the adhesive force between the photosensitive resin composition layer 2 and the protective film 3 is preferably small, and a polymer can be used. Olefin-based films such as ethylene and polypropylene, and polyester films represented by polyethylene terephthalate. When a polyester film is used as the support body 1 and the same type of polyester film is used for the protective film 3, it is preferable to use the protective film 3 processed on the surface in contact with the photosensitive resin composition layer.

In addition, these protective films 3 are preferably low fisheye films. Here, "fish eye" refers to the incorporation of foreign matter, unmelted matter, oxidative deterioration, etc. situation in the film. That is, "low fisheye" means that there are few foreign substances and the like in the film.

Further, in the photosensitive element 10, in addition to the photosensitive resin composition layer 2, the support body 1, and the optional protective film 3, intermediate layers such as buffer layers, adhesive layers, light-absorbing layers, and gas barrier layers may be included, The protective layer.

The produced photosensitive element 10 is usually wound up on a cylindrical core and stored. Here, at this time, it is preferable to wind up so that the support body 1 may become the outer side. On the end surface of the rolled photosensitive element roll, an end surface separator is preferably provided from the viewpoint of end surface protection, and a moisture-proof end surface separator is preferably provided from the viewpoint of edge fusion resistance. The fringe mentioned here means the phenomenon in which the photosensitive resin composition layer 2 also called cold flow seeps out from an end surface. When this phenomenon occurs, it becomes a source of generation of foreign matter at the time of forming the partition wall, which is an undesirable phenomenon. In addition, as a packing method, it is preferable to pack by wrapping in a black sheet (black sheet) which has low moisture permeability and is excellent in light-shielding properties. Examples of the material of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

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

Next, the formation method of the partition wall of the image display apparatus using the photosensitive resin composition of this invention or a photosensitive element, the manufacturing method of an image display apparatus, and an image display apparatus are demonstrated.

First, as shown in FIG. 2( a), an electrode substrate 30 including the electrodes 4 and a substrate 5 is prepared. As shown in FIG. 2( b), the photosensitive resin in the above-mentioned photosensitive element 10 is laminated on the electrode substrate 30. Composition layer 2 and support body 1 (lamination process).

The substrate 5 constituting the electrode substrate 30 is not particularly limited if it is a flexible substrate, and examples thereof include insulating substrates such as polymer film substrates and semiconductor substrates such as silicon substrates. As the electrode substrate 30 , an electrode substrate in which a flexible electrode 4 such as ITO, IZO, or Ag wire ink is formed on such a substrate 5 is exemplified. The method of forming the electrode 4 includes a method of patterning an electrode material stacked by vapor deposition, sputtering, etc. using a photolithography technique, a method of patterning a photosensitive electrode material, and the like. The method of forming this electrode 4 is not particularly limited.

As a lamination method for laminating the photosensitive resin composition layer 2 on the electrode substrate 30, in addition to the method of using the above-mentioned photosensitive element 10, it is also possible to apply a solution of the photosensitive resin composition on the electrode substrate 30 and drying method.

Regarding the lamination method using the photosensitive element 10 , when the protective film 3 exists on the photosensitive resin composition layer 2 , it is laminated on the electrode substrate 30 while removing the protective film 3 . As the above-mentioned lamination conditions, for example, while heating the photosensitive resin composition layer 2 at about 70-130° C., it is pressure-bonded to the electrode substrate 30 under a pressure of about 0.1-1 MPa (about 1-10 kgf/cm ² ). Therefore, in the method of lamination, etc., lamination under reduced pressure is also possible. The shape of the surface of the electrode substrate 30 is usually formed with an electrode pattern, and may be flat, or may be uneven as needed.

After lamination of the photosensitive resin composition layer 2 , as shown in FIG. 2( b ), the photosensitive resin composition layer 2 is irradiated with active light 8 in an image form to photocure the exposed portion (exposure step). As a method of irradiating active light rays 8 in image form, as shown in FIG. A method for photocuring the permanent resin composition layer 2. The mask pattern 7 may be a negative type or a positive type, and a generally used mask pattern can be used. As the light source of the actinic light 8, known light sources such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, and xenon lamps that efficiently emit ultraviolet rays, visible light, and the like can be used. In addition, as an exposure method, a direct drawing exposure method in which a pattern is directly drawn by a laser without using the mask pattern 7 can also be used.

After exposure, as shown in FIG. 2( c), the photosensitive resin composition layer 2 in the unexposed portion is selectively removed by development, thereby forming a photocured product pattern on the substrate (electrode substrate 30) for the image display device. 20 (developing process). Here, regarding the image development step, when the support body 1 is present, the support body 1 is removed before image development.

Image development is performed by removing an unexposed part by wet image development, dry image development, etc. with a developer, such as an alkaline aqueous solution, an aqueous developer, and an organic solvent. In the present invention, an alkaline aqueous solution is preferably used. As an alkaline aqueous solution, the dilute solution of 0.1-5 mass % of sodium carbonate, the dilute solution of 0.1-5 mass % of potassium carbonate, the dilute solution of 0.1-5 mass % of potassium hydroxide etc. are mentioned, for example. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. In addition, a surfactant, an antifoaming agent, an organic solvent, and the like may be mixed with the alkaline aqueous solution. Examples of the image development method include dipping, spraying, brushing, and tapping, but the spraying method is preferable for improving resolution.

As the treatment after development, it is preferable to further cure the formed photo-cured product pattern 20 by heat treatment at about 60 to 250° C. as necessary. The curing temperature is preferably about 80 to 200°C, more preferably about 100 to 150°C. In addition, the curing time is not particularly limited, but is preferably 10 minutes to 3 hours, more preferably 30 minutes to 2 hours.

In addition, through the process of filling the display medium such as particles in the photo-cured product pattern 20 formed by the above steps, and the process of attaching another electrode substrate 30 on the photo-cured product pattern 20 (Fig. 2(d) and (e) )) etc., thereby completing the formation of the partition wall of the image display device and the manufacture of the image display device.

The step of sticking the other electrode substrate 30 on the photo-cured product pattern 20 can be performed as follows. That is, the above steps are carried out as follows: as shown in Figure 2 (d), by laminating the adhesive 40 on the photocured pattern 20, as shown in Figure 2 (e), the electrode substrate 30 and the photo The cured product pattern 20 is bonded. Here, a transparent electrode substrate can be used for at least the electrode substrate on the display surface side of the image display device.

The image display device formed through the above steps includes the flexible electrode substrate 30 and the partition wall formed of the photocured pattern 20 with high elongation, and can achieve excellent flexibility. In particular, depending on the selection of the material of the electrode 4, an image display device having a high degree of bendability capable of realizing a curvature radius of about 5 to 15 mm can be obtained. Moreover, even when the partition formed using the photosensitive resin composition of this invention bends an image display apparatus with a curvature radius of about 5-15 mm, generation|occurrence|production of damage can fully be suppressed.

Example

Hereinafter, the present invention will be specifically described through examples. However, the present invention is not limited to these examples as long as it does not deviate from the technical idea of the present invention.

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

After mixing the (A) component, (B) component, (C) component, (E) component, and other components shown in Table 1, the (D) component shown in Table 1 was added thereto and dissolved to obtain The photosensitive resin compositions of Examples 1-4 and Comparative Examples 1-5 were obtained. Table 1 shows the compounding quantity (unit: g) of each component.

Table 1

The details of each component in Table 1 are as follows. Here, about (A) component, the following quantity was mix|blended as a resin solution, and the quantity of solid content is shown in Table 1.

(A) Component: Binder polymer

*1: 48% by mass methyl cellosolve of methacrylic acid/methyl methacrylate/butyl methacrylate copolymer (resin A, mass ratio 30/35/35, weight average molecular weight 50000, acid value 196) /toluene (mass ratio 6/4) solution 93.75g (solid matter 45g)

*2: 48% by mass of methacrylic acid/methyl methacrylate/benzyl methacrylate/styrene copolymer (resin B, mass ratio 30/5/25/40, weight average molecular weight 56000, acid value 196) Methyl cellosolve/toluene (mass ratio 6/4) solution 93.75g (solid matter 45g)

(B) Component: Photopolymerizable compound

*3: A photopolymerizable compound obtained by reacting a polycarbonate compound having a terminal hydroxyl group, an organic isocyanate, and 2-hydroxyethyl acrylate (weight average molecular weight 4000, manufactured by Hitachi Chemical Industries, Ltd., trade name: HT -9082-95)

*4: UA-21EB (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name)

*5: FA-023M (manufactured by Hitachi Chemical Industries, Ltd., brand name)

*6: FA-024M (manufactured by Hitachi Chemical Industries, Ltd., brand name)

*7: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-phthalate (manufactured by Hitachi Chemical Industries, Ltd., brand name: FA-MECH)

(C) Component: Photopolymerization Initiator

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

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

*10: 1,7-bis(9-acridyl)heptane (manufactured by ADEKA, trade name: N-1717)

*11: benzil dimethyl ketal (manufactured by Ciba Specialty Chemicals, trade name: I-651)

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

*12: Cresol novolak type epoxy resin (manufactured by DIC Corporation, brand name: EPICLONN-670-EXP-S)

*13: Dicyclopentadiene-type epoxy resin (manufactured by DIC Corporation, brand name: EPICLONHP-7200L)

*14: Bisphenol A epoxy resin (manufactured by DIC Corporation, brand name: EPICLON1055)

*15: Cresol novolak type epoxy resin (manufactured by DIC Corporation, brand name: EPICLONN-665-EXP)

Blocked isocyanate compound

*16: Blocked isocyanate (manufactured by Sumitomo Bayer Polyurethane Co., Ltd., trade name: SumidurBL3175)

*17: Blocked isocyanate (manufactured by Sumitomo Bayer Polyurethane Co., Ltd., trade name: Desmodur BL3475)

*18: Blocked isocyanate (manufactured by Sumitomo Bayer Polyurethane Co., Ltd., trade name: DesmodurVPLS2253)

(E) Component: Inorganic black pigment

*19: Titanium black dispersion (manufactured by Japan Excel-Management Consulting Co., Ltd., trade name: BT-1HCA)

other ingredients

*20: Pigment dispersant (manufactured by Kyoeisha Chemical Co., Ltd., trade name: FLOWLENDOPA-17HF)

*21: Methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd., trade name: SZ-6030)

Next, the solution of the obtained photosensitive resin composition was uniformly coated on a polyethylene terephthalate film (manufactured by Teijin DuPont Film Co., Ltd., trade name: HTR-02) with a thickness of 16 μm. °C hot air convection dryer for 10 minutes to form a photosensitive resin composition layer. Thereafter, the photosensitive resin composition was coated with a polyethylene protective film (tensile strength in the longitudinal direction of the film: 16 MPa, tensile strength in the width direction of the film: 12 MPa, manufactured by TAMAPOLY CO., LTD., trade name: NF-15) layer protection, the photosensitive element is obtained. The film thickness of the photosensitive resin composition layer after drying was 45 micrometers.

On the ITO surface of a PET base material with ITO (manufactured by Toyobo Co., Ltd., trade name: R-300), the above-mentioned photosensitive element is made to contact the photosensitive resin composition layer with the PET base material with ITO. Lamination was carried out with lamination rolls heated to 110°C while peeling off the protective film made of polyethylene. The configuration of the obtained laminate was, from the bottom, an ITO-attached PET substrate, a photosensitive resin composition layer, and a polyethylene terephthalate film. The obtained laminate was evaluated for sensitivity, adhesiveness, resolution, and seaming.

＜Evaluation of Sensitivity＞

Using a collimated light exposure machine EXM-1201 (manufactured by ORC Manufacturing Co., Ltd.) with a high-pressure mercury lamp, a phototool (phototool) with a 41-grid exposure ruler is closely attached to the polyethylene terephthalate film of the laminate, Exposure was made. After exposure, the polyethylene terephthalate film was peeled off, and 1 mass % sodium carbonate aqueous solution was sprayed at 30 degreeC for 20 second, and the unexposed part of the photosensitive resin composition layer was removed. The amount of energy (exposure amount) at which the number of remaining frames after development of the 41-frame exposure scale becomes 29.0 was defined as sensitivity (mJ/cm ² ). The smaller the numerical value of the amount of energy, the higher the sensitivity. Table 2 shows the evaluation results. In addition, Table 2 shows the actual number of remaining frames when exposure was performed with the amount of energy described above.

＜Evaluation of Adhesiveness＞

Using a collimated light exposure machine EXM-1201 (manufactured by ORC Manufacturing Co., Ltd.) equipped with a high-pressure mercury lamp, a wiring pattern having a line width/space width of 10/300 to 80/300 (unit: μm, constant space width) was used as a bonding pattern. The optical tool of the negative film for performance evaluation, and the optical tool with 41-scale exposure scale are closely attached to the laminated polyethylene terephthalate film, and the number of remaining frames after development with 41-scale exposure scale becomes 29.0 energy amount of exposure. After exposure, the polyethylene terephthalate film was peeled off, and 1 mass % sodium carbonate aqueous solution was sprayed at 30 degreeC for 20 second, and the unexposed part of the photosensitive resin composition layer was removed, and the adhesiveness was evaluated. Adhesiveness is represented by the width (μm) of the smallest line that remains without peeling off under the action of the developer. The smaller the value, the tighter the line without peeling off from the glass substrate. Therefore, the adhesiveness higher. Table 2 shows the evaluation results.

＜Evaluation of resolution＞

An optical tool with a 41-grid exposure ruler and an optical tool with a wiring pattern with a line width/space width of 30/30 to 200/200 (unit: μm) as a negative film for resolution evaluation are closely bonded to the laminated pair On the ethylene phthalate film, using a collimated light exposure machine EXM-1201 (manufactured by ORC Manufacturing Co., Ltd.) equipped with a high-pressure mercury lamp, it was carried out at an amount of energy at which the number of remaining frames after development of a 41-frame exposure scale became 29.0. exposure. After exposure, the polyethylene terephthalate film was peeled off, a 1 mass % sodium carbonate aqueous solution was sprayed at 30 degreeC for 20 seconds, and the unexposed part of the photosensitive resin composition layer was removed, and the resolution was evaluated. The resolution is represented by the minimum space width (μm) at which the unexposed portion can be well removed by the developing process, and the smaller this numerical value is, the better the resolution is.

Table 2 shows the evaluation results.

＜Crimming test＞

Using parallel light exposure machine EXM-1201 (manufactured by ORC Manufacturing Co., Ltd.) equipped with a high-pressure mercury lamp, it exposed with the amount of energy at which the number of remaining frames after development of 41 exposure scales becomes 29.0. After exposure, the polyethylene terephthalate film was peeled off, and 1 mass % sodium carbonate aqueous solution was sprayed at 30 degreeC for 20 second, and the unexposed part of the photosensitive resin composition layer was removed. Next, it was left still for 1 hour in a box-type dryer (manufactured by Mitsubishi Electric Corporation, model: NV50-CA, air atmosphere) heated to 120°C. The obtained evaluation sheets were crimped, and the case where the cured product of the photosensitive resin composition layer did not peel off from the ITO-coated PET base material was designated as A, and the case where the cured product of the photosensitive resin composition layer was found to be from the ITO-coated PET substrate The case where the PET base material peeled off or the case where damage was recognized was set as B.

＜Solubility of electrodes＞

On the IZO and ITO surfaces of the IZO-TEG (TestElementGroup) substrate and the ITO-TEG (TestElementGroup) substrate, the above-mentioned photosensitive element is connected to the IZO-TEG substrate and the ITO-TEG substrate according to the following steps: In the form of the surface, the protective film made of polyethylene was laminated with a laminating roll heated to 110°C. The configuration of the obtained laminate was a TEG substrate, a photosensitive resin composition layer, and a polyethylene terephthalate film from the bottom. A light tool with a 41-grid exposure scale was closely bonded to the polyethylene terephthalate film of the laminate, and a parallel light exposure machine EXM-1201 (manufactured by ORC Manufacturing Co., Ltd.) with a high-pressure mercury lamp was used to develop Exposure is performed with the amount of energy at which the number of remaining frames becomes 29.0. After exposure, the polyethylene terephthalate film was peeled off, and a 1 mass % sodium carbonate aqueous solution was sprayed at 30 degreeC for 20 second, and the unexposed part of the photosensitive resin composition layer was removed. Thus, an evaluation substrate in which a photocured product of a photosensitive resin composition layer was formed on a TEG substrate was obtained. Next, the obtained evaluation substrate was left still for 1 hour in a box-type dryer (manufactured by Mitsubishi Electric Corporation, model: NV50-CA) heated to 120°C. Thereafter, under the conditions of 60° C. and 90% RH, a DC voltage of 80 V was applied to the electrodes of the evaluation substrate, and the resistance value of the anode after 100 hours was measured with a tester. Table 2 shows the evaluation results. In the table, A indicates the case where the measurement of the resistance value was possible and it was judged that there was no disconnection due to melting, and B indicates the case where the measurement was not possible and it was judged that there was a disconnection due to melting. In addition, regarding A, the value obtained by dividing the resistance value of the anode after 100 hours by the initial resistance value and multiplying by 100 times was described as the resistance improvement rate (%). It can be evaluated that melting of the electrode can be suppressed so much that the value of the resistance increase rate is small.

＜Elongation of cured product＞

On a polytetrafluoroethylene sheet (manufactured by Nitto Denko Co., Ltd., product name: Nitoflonfilm No. 900U), the photosensitive element was placed in such a way that the photosensitive resin composition layer was in contact with the surface of the polytetrafluoroethylene sheet. , while peeling off the protective film made of polyethylene, it was laminated with a laminating roll heated to 110°C. The structure of the obtained laminate was the order of a polytetrafluoroethylene sheet, a photosensitive resin composition layer, and a polyethylene terephthalate film. Exposure was performed from the polyethylene terephthalate film of the above-mentioned laminate using a parallel light exposure machine EXM-1201 (manufactured by ORC Manufacturing Co., Ltd.). Here, at the time of exposure of the laminated product, the amount of energy is set so that the number of remaining frames after development of the 41-frame exposure scale becomes 29.0. After exposure, the polyethylene terephthalate film was peeled off, and a 1 mass % sodium carbonate aqueous solution was sprayed at 30 degreeC for 30 second, and the unexposed part of the photosensitive resin composition layer was removed. Thus, an evaluation sheet obtained by forming a photocured product of a photosensitive resin composition layer on a polytetrafluoroethylene sheet was obtained. Next, the obtained evaluation sheet was left still for 1 hour in a box-type dryer (manufactured by Mitsubishi Electric Corporation, model: NV50-CA, air atmosphere) heated to 120°C. Cut the evaluation sheet after heat treatment into a width of 10 mm, set the chuck distance to 50 mm, and stretch it at a constant speed of 2 cm/min until the cured product of the photosensitive resin composition layer breaks. The elongation (%) of the cured product. Table 2 shows the evaluation results.

Table 2

From the results shown in Table 2, it was clearly confirmed that melting of the electrode was suppressed due to the presence of the component (D). In addition, regarding elongation, it was confirmed that a height elongation of 40% or more was obtained, and breakage of the partition wall during bending was suppressed.

Industrial availability

As described above, according to the present invention, it is possible to provide a photosensitive resin composition capable of suppressing melting of an electrode when a voltage is applied under high temperature and high humidity and forming a partition wall for an image display device capable of suppressing damage during bending, A photosensitive element using the same, a method for forming a partition of an image display device, a method for manufacturing an image display device, and an image display device.

Explanation of reference signs

1 is a support, 2 is a photosensitive resin composition layer, 3 is a protective film, 4 is an electrode, 5 is a substrate, 10 is a photosensitive element, 20 is a cured product of the photosensitive resin composition (photocured product pattern), 30 is an electrode substrate, and 40 is an adhesive.

Claims (10)

1. A photosensitive resin composition, which is a photosensitive resin composition for forming a partition wall separating pixels in an image display device, the image display device having a flexible transparent electrode at least on a display surface image display device, The photosensitive resin composition contains (A) component: a binder polymer having a carboxyl group in a molecule, (B) component: a photopolymerizable compound, (C) component: a photopolymerization initiator, and (D) component : A compound having an epoxy group in the molecule, After photocuring the photosensitive resin composition, the elongation at 25° C. of a sheet-like cured product having a width of 10 mm and a thickness of 45 μm obtained by heating at 120° C. for 1 hour in air was 40% or more. 2. The photosensitive resin composition according to claim 1, further comprising (E) component: an inorganic black pigment. 3. The photosensitive resin composition according to claim 2, wherein the component (E) contains titanium black. A photosensitive element comprising a support body and a photosensitive resin composition layer formed on the support body formed from the photosensitive resin composition according to any one of claims 1 to 3. 5. A method for forming a partition wall of an image display device, which is a method for forming a partition wall of an image display device having flexibility, comprising at least a transparent electrode disposed on a display surface and a partition wall separating pixels, The method for forming the partition wall of the image display device has the following steps: a lamination step of laminating a photosensitive resin composition layer formed of the photosensitive resin composition according to any one of claims 1 to 3 on the substrate of the image display device, an exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with active light to photocure the exposed portion, In the developing step, a part of the photosensitive resin composition layer other than the exposed part is removed to form a photocured product pattern. 6. A method of manufacturing an image display device, which is a method of manufacturing a flexible image display device provided with at least a transparent electrode disposed on a display surface and a partition wall separating pixels, the method of manufacturing the image display device It has the process of forming the said partition wall by the method of Claim 5. 7. The method of manufacturing an image display device according to claim 6, wherein the transparent electrode is made of a material formed by coating a solution containing at least one metal conductive fiber. 8. The method for manufacturing an image display device according to claim 6 or 7, further comprising the steps of: a step of filling the partition wall with a display medium, A process of affixing a substrate on the side opposite to the partition wall so as to face one of the substrates. 9. An image display device manufactured by the manufacturing method according to any one of claims 6 to 8. 10. An application of a photosensitive resin composition for forming a partition wall separating pixels in an image display device, the image display device being a flexible image having a transparent electrode at least on a display surface display device, The photosensitive resin composition contains (A) component: a binder polymer having a carboxyl group in a molecule, (B) component: a photopolymerizable compound, (C) component: a photopolymerization initiator, and (D) component : A compound having an epoxy group in the molecule, After photocuring the photosensitive resin composition, the elongation at 25° C. of a sheet-like cured product having a width of 10 mm and a thickness of 45 μm obtained by heating at 120° C. for 1 hour in air was 40% or more.