JP2012018410A - Photosensitive resin composition, photosensitive element using the same, method for forming barrier wall of image display device, method for manufacturing image display device, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of suppressing dissolution of an electrode and forming a barrier wall that can suppress breakage during bending.SOLUTION: The photosensitive resin composition is used to form a barrier wall for separating pixels in an image display device having flexibility, including a transparent electrode on at least a display surface. The photosensitive resin composition contains components of (A) a binder polymer having a carboxyl group in the molecule, (B) a photopolymerizable compound, (C) a photopolymerization initiator and (D) a compound having an epoxy group in the molecule. When a sheet-like cured product having a width of 10 mm and a thickness of 45 μm is prepared by photo-curing the photosensitive resin composition and heating the cured product in air at 120°C for 1 hour, the prepared cured product shows an elongation rate of 40% or more at 25°C.

Description

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

  2. Description of the Related Art In recent years, an image display device (PLD: Paper Like Display) that is as thin as paper, can be freely carried, and can display characters and images has attracted attention. Such an image display device has visibility and portability, which are the advantages of paper as a normal printed matter, and is capable of electrically rewriting information, so that it can be used as a substitute for paper from the viewpoint of environment and cost. Practical application is being attempted.

  As a display technique of the image display device, various types such as a type in which particles are moved by electrophoresis or the like, a liquid crystal type, and an electrochemical type have been devised (for example, see Non-Patent Document 1). In particular, as a type 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 systems, white and black particles as a display medium are sealed between transparent electrodes, an electric field is applied, and these particles are electrically moved to form and display a white / black image. In addition, there are active driving and passive driving as driving methods of the image display device, and a back technology (panel circuit) for the image display device has been studied.

  In the case of the particle movement type image display device, a partition wall for enclosing white / black particles as described above is required. As a method for forming such partition walls, a mold transfer method, a screen printing method, a sand blast method, a photolithography method, an additive method, and the like have been proposed (for example, see Patent Document 1). Among these, a photolithographic method that can form a high-definition pattern efficiently by irradiation with actinic rays using a photosensitive resin composition has attracted attention.

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

  When the image display apparatus is made flexible, the flexibility of the electrode substrate is essential. Conventionally, ITO (Indium Tin Oxide) used as a transparent electrode has poor flexibility, and in recent years, ITO alternatives such as IZO (Indium Zinc Oxide), Ag wire ink, and organic conductive materials have been studied. (For example, see Non-Patent Document 3). Various degrees of flexibility have been studied, from those that can be flexed to those that can be rounded down and reduced in volume when carried. As the radius of curvature in the case of small rounding, about 15 to 20 mm, which is the limit of the flexibility of the ITO electrode substrate, is generally assumed, but about 5 to 15 mm for Ag wire ink, organic conductive material, and combinations thereof. The radius of curvature can be reduced up to.

  Further, when performing full color display, a color filter is used in combination with a white / black display image display device, and thus it is essential to improve the contrast between pixels. Therefore, a light shielding layer for shielding light between the pixels is required. In the case of monochrome display, in order to increase the brightness of the image of the image display device without using a color filter, transparency rather than light shielding properties may be required.

  The partition walls of the image display device using the photolithography method are formed as follows. That is, a step of laminating a light shielding layer called a black matrix on a substrate by photolithography technology, and further forming a photosensitive resin composition layer by applying a photosensitive resin composition on the light shielding layer or laminating a photosensitive element. And a step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photocure the exposed portion and a step of removing the unexposed portion to form a photocured product pattern. Note that a light shielding layer called a black matrix may be omitted. Therefore, in general, the photosensitive resin composition for forming the partition walls of the image display device is required to have sensitivity, resolution, and adhesion to the substrate.

  Further, when manufacturing an image display device, a step of filling a display medium such as particles in the photocured product pattern obtained in the above step, a step of heat-treating the photocured product pattern, a step of attaching an electrode substrate, etc. In addition. Thereby, the image display apparatus which uses the hardened | cured material of the photosensitive resin composition layer as a partition is obtained.

JP 2007-178881 A

Akira Suzuki, “Latest Trends in Electronic Paper 2007”, October 10, 2007, Journal of the Imaging Society of Japan, Vol. 46, No. 5: 372-384 (2007) Tanuma Itsuo, “Flexible Electronic Paper Using Electron Powder Fluid”, October 10, 2007, Journal of the Imaging Society of Japan, Vol. 46, No. 5: 396-400 (2007) Satoshi Nezu, “Introducing new materials into transparent electrodes”, August 10, 2009, Nikkei Electronics 59-65 (2009)

  In the process of affixing the electrode substrate, a voltage is applied under high temperature and high humidity, so that there is a possibility that the electrode portion in close contact with the cured product of the photosensitive resin composition is dissolved. Actually, IZO, which has been studied as a flexible electrode substrate, contains amphoteric metal zinc, so that it has a problem of being dissolved in the step of attaching the electrode substrate. Furthermore, when an electrode material having a high degree of flexibility and capable of dealing with a curvature radius of about 5 to 15 mm, such as Ag wire ink, an organic conductive material, or a combination thereof, is used when the partition wall material is bent There was a problem of being damaged.

  Therefore, the present invention has been made in view of the above problems, and a photosensitive resin composition capable of forming a partition wall that can suppress dissolution of an electrode and suppress breakage during bending, and a photosensitive resin using the same. It is an object to provide a conductive element, a method for forming a partition wall of an image display device, a method for manufacturing the image display device, and an image display device.

  In order to achieve the above object, the present invention provides a photosensitive resin composition for forming a partition separating pixels in a flexible image display device having a transparent electrode on at least a display surface, The photosensitive resin composition comprises (A) component: binder polymer having a carboxyl group in the molecule, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: molecule. A sheet-like cured product having a width of 10 mm and a thickness of 45 μm, comprising a compound having an epoxy group therein, photocuring the photosensitive resin composition, and heating at 120 ° C. for 1 hour in air, A photosensitive resin composition having an elongation at 25 ° C. of 40% or more is provided.

  According to the photosensitive resin composition having the above-described configuration, it is possible to form a partition that can suppress breakage during bending while suppressing dissolution of the electrode, which is a problem when forming the partition of the image display device. Moreover, according to the said photosensitive resin composition, the photocured material pattern excellent in the resolution and adhesiveness can be formed with a sufficient sensitivity. Although the detailed reason why dissolution of the electrode is suppressed by the photosensitive resin composition having the above configuration is not clear, the (D) component traps the carboxyl group remaining in the cured product of the photosensitive resin composition. It is thought that dissolution of the electrode is suppressed. In addition, the breakage of the partition walls at the time of bending is suppressed by reducing the crosslink density of the cured product of the photosensitive resin composition and adjusting the elongation rate to be in the above range, thereby bending the image display device. This is considered to be because it is possible to follow the elongation without breaking the partition wall. 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 that can sufficiently suppress the occurrence of breakage.

  The photosensitive resin composition of the present invention may further contain (E) component: an inorganic black pigment. Moreover, it is preferable that the said (E) component contains titanium black. By containing the component (E), the conflicting characteristics of photosensitivity and light shielding property can be maintained in a well-balanced manner. On the other hand, in order to improve the brightness of the image display device, there is a case where a photosensitive resin composition for forming a partition wall containing no inorganic black pigment (component (E)) and a photosensitive element using the same are required. Therefore, what is necessary is just to add (E) component as needed.

  The present invention also provides a photosensitive element comprising a support and a photosensitive resin composition layer comprising the above-described 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 that can suppress breakage at the time of bending while suppressing dissolution of the electrode, which is a problem when forming the partition wall of the image display device. Moreover, according to this photosensitive element, the photocured material pattern excellent in the resolution and the adhesiveness can be formed with high sensitivity.

  The present invention is also 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 for separating pixels, on the substrate of the image display device, A lamination step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention, and an exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photocure an exposed portion; And a developing step of forming a photocured product pattern by removing a portion other than the exposed portion of the photosensitive resin composition layer.

  The present invention further relates to a method for manufacturing a flexible image display device comprising at least a transparent electrode disposed on a display surface and a partition wall for separating pixels, and the partition wall of the image display device according to the present invention is formed. Provided is a method for manufacturing an image display device, comprising the step of forming the partition wall by a method.

  According to the method for forming the partition wall of the image display device and the method for manufacturing the image display device, since the partition wall is formed by the above-described photosensitive resin composition of the present invention, dissolution of the electrode when forming the partition wall is suppressed. In addition, a partition wall that can suppress breakage during bending can be formed.

  In the method for manufacturing an image display device, the transparent electrode is preferably made of a material formed by applying a solution containing at least one type of metal conductive fiber. Thereby, the image display apparatus which has the outstanding flexibility which can respond to a curvature radius of about 5-15 mm can be formed. Examples of the electrode material include Ag wire and ink.

  Moreover, it is preferable that the manufacturing method of the said image display apparatus further includes the process of filling a display medium in the said partition, and the process of affixing a board | substrate on the opposite side of a partition so as to oppose one board | substrate.

  The present invention also provides an image display device manufactured by the manufacturing method described above. Since these image display devices are manufactured by the above-described manufacturing method, the dissolution of the transparent electrode is suppressed, and a partition wall that can suppress breakage during bending is provided, and the reliability of the device is increased.

  According to the present invention, a photosensitive resin composition capable of forming a partition for an image display device capable of suppressing breakage during bending while suppressing dissolution of an electrode when a voltage is applied under high temperature and high humidity, The photosensitive element using this, the formation method of the partition of an image display apparatus, the manufacturing method of an image display apparatus, and an image display apparatus can be provided.

It is a schematic cross section which shows suitable one Embodiment of the photosensitive element of this invention. It is a schematic cross section for demonstrating one Embodiment of the formation method of the partition of the image display apparatus using the photosensitive element of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In the present specification, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, and (meth) acryloyl means acryloyl and it. Means the corresponding methacryloyl.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention is a photosensitive resin composition for forming a partition for separating pixels in a flexible image display device having a transparent electrode on at least a display surface, wherein (A) Component: Contains a binder polymer having a carboxyl group in the molecule, (B) component: a photopolymerizable compound, (C) component: a photopolymerization initiator, and (D) component: a compound having an epoxy group in the molecule. And after photocuring the said photosensitive resin composition, the elongation rate in 25 degreeC of the sheet-like hardened | cured material of width 10mm and thickness 45micrometer formed by heating at 120 degreeC in air for 1 hour is 40% or more. It is characterized by being.

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

(A) component: binder polymer having a carboxyl group in the molecule (A) component 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 thereof include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, and urethane resins. Among these, acrylic resins are preferable from the viewpoint of alkali developability. These can be used alone or in combination of two or more. Examples of combinations of two or more types of binder polymers include two or more types of binder polymers composed of different copolymer components, two or more types of binder polymers having different weight average molecular weights, two or more types of binder polymers having different degrees of dispersion, and the like. Can be mentioned. A polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used. In addition, the binder polymer may have a photosensitive group as necessary.

  The component (A) can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer. Examples of the polymerizable monomer include styrene; polymerizable styrene derivatives such as vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; vinyl alcohol such as vinyl-n-butyl ether. (Meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2 , 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) Acrylic acid, β-furyl (meth) (Meth) acrylic monomers such as crylic acid, β-styryl (meth) acrylic acid; maleic acid; maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester Examples include acid monoesters; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. As the polymerizable monomer having a carboxyl group, (meth) acrylic acid is preferred from the viewpoints of developability and stability. Moreover, these can be used as a homopolymer alone or in combination of two or more as a copolymer.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, heptyl (meth) 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 excellent developability and resolution.

  The acid value of the component (A) is preferably 30 mgKOH / g or more, more preferably 80 mgKOH / g or more, further preferably 130 mgKOH / g or more, and 180 mgKOH / g or more in terms of excellent resolution. It is particularly preferred that In terms of excellent developer resistance and adhesion, it is preferably 250 mgKOH / g or less, more preferably 240 mgKOH / g or less, further preferably 230 mgKOH / g or less, and 220 mgKOH / g or less. It is particularly preferred. In addition, when developing with a solvent as a development process, it is preferable to prepare by suppressing the usage-amount of the polymerizable monomer which has a carboxyl group.

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

A = 10 × Vf × 56.1 / (Wp × I)
In the formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of a 0.1N KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I was measured. The ratio (mass%) of the non volatile matter in a resin solution is shown.

  The weight average molecular weight of component (A) (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) is 20,000 or more in terms of excellent developer resistance. Preferably, it is 25,000 or more, more preferably 30,000 or more. From the viewpoint of shortening the development 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 gel permeation chromatography and converted using a standard polystyrene calibration curve. The measurement conditions of gel permeation chromatography (GPC) are as shown below.

[GPC measurement conditions]
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R420 + Gelpack GL-R430 +
Gelpack GL-R440 (three in total) (above, manufactured by Hitachi Chemical Co., Ltd., trade name) Eluent: Tetrahydrofuran Measurement temperature: 25 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

  The content of the component (A) in the photosensitive resin composition is 40 parts by mass in terms of excellent coating properties of the photosensitive resin composition with respect to 100 parts by mass of the total amount of the components (A) and (B). The above is preferable, and 45 parts by mass or more is more preferable. In the point which is excellent in the mechanical strength of a photocured material, 70 mass parts or less are preferable with respect to 100 mass parts of total amounts of (A) component and (B) component, and 60 mass parts or less are more preferable.

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

Component (B1): Compound having an ethylenically unsaturated group and a urethane bond in the molecule It is preferable that component (B1) is included in that the elongation of the cured product can be improved and the adhesiveness to the flexible substrate is excellent. .

  Although there is no restriction | limiting in particular as (B1) component which can be used for this invention, It is preferable to contain the compound which has an isocyanuric ring structure. As a compound which has an isocyanuric ring structure, the compound represented by following General formula (1) is mentioned, for example.

［式（１）中、Ｒ^１は各々独立に、下記一般式（２）で表される基、下記一般式（３）で表される、又は、下記一般式（４）で表される基を示し、Ｒ^１のうち少なくとも１つは下記一般式（４）で表される基である。］

[In the formula (1), each R ¹ is independently 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). And at least one of R ¹ is a group represented by the following general formula (4). ]

［式（２）中、Ｒ^２は水素原子又はメチル基を示し、ｍは１〜１５の整数を示す。］

[In formula (2), ^{R 2} represents a hydrogen atom or a methyl group, m is an integer of 1 to 15. ]

［式（３）中、ｍは１〜１５の整数である。］

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

［式（４）中、Ｒ^２は水素原子又はメチル基を示し、ｎは１〜９の整数を示し、ｍは１〜１５の整数を示す。］

Wherein (4), ^{R 2} represents a hydrogen atom or a methyl group, n represents an integer of 1 to 9, m is an integer of 1 to 15. ]

From the viewpoint of elastic modulus and adhesion, at least two of R ^{1 in} the general formula (1) are more preferably groups represented by the general formula (4), and all of R ¹ are represented by the general formula. A group represented by (4) is more preferable.

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

Examples of commercially available compounds represented by the above general formula (1) include, for example, NK Oligo UA-21EB (Shin Nakamura Chemical Co., Ltd., trade name, general formula (1), wherein R ¹ is all represented by the general formula Compound (4)).

  In addition, as the component (B1), a urethane compound having a urethane bond derived from a reaction between a hydroxyl group at a terminal of a polycarbonate compound and / or a polyester compound and an isocyanate group of a diisocyanate compound, and having an isocyanate group at a plurality of terminals And a compound that can be obtained by a condensation reaction of a compound having a hydroxyl group and an ethylenically unsaturated group.

  As these compounds, those synthesized by a conventional method may be used, or commercially available ones may be used. Examples of commercially available products include UF-8003M, UF-TCB-50, UF-TC4-55 (trade names, manufactured by Kyoeisha Chemical Co., Ltd.) and HT9082-95 (trade names, manufactured by Hitachi Chemical Co., Ltd.). Can be mentioned.

  Furthermore, as the component (B1) other than the above, for example, a (meth) acryl monomer having a hydroxyl group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexa Addition reaction products with diisocyanate compounds such as methylene diisocyanate; EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate. Examples of the EO-modified urethane di (meth) acrylate include product name UA-11 manufactured by Shin-Nakamura Chemical Co., Ltd. Examples of the EO and PO-modified urethane di (meth) acrylate include product name UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd.

Component (B2): Compound obtained by reacting polyhydric alcohol and / or glycidyl group-containing compound with α, β-unsaturated carboxylic acid (B2) As component, for example, polyethylene glycol di (meth) acrylate (ethylene group) Polyalkylene glycol di (meth) acrylates such as polypropylene glycol di (meth) acrylate (having 2 to 14 propylene groups); trimethylolpropane di (meth) acrylate, tri Trimethylolpropane (meth) acrylate compounds such as methylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane propoxytri (meth) acrylate; tetramethylolmethane tri (meth) acrylate, Tetramethylolmethane (meth) acrylate compounds such as lamethylolmethane tetra (meth) acrylate; dipentaerythritol (meth) acrylate compounds such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; bisphenol A di Bisphenol A dioxyethylene di (meth) acrylate such as oxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate; trimethylolpropane triglycidyl ether triacrylate And bisphenol A diglycidyl ether acrylate.

  Especially, it is preferable to contain polyalkylene glycol di (meth) acrylate as (B2) component in the point which is excellent in the resolution and adhesiveness, maintaining the low elasticity of a cured film, and the following general formula (5), (6 It is more preferable that the compound represented by (7) or (7) is included.

In said general formula (5), (6) or (7), R shows a hydrogen atom or a methyl group each independently, EO shows an oxyethylene group, PO shows an oxypropylene group. m ₁ , m ₂ , m ₃ and m ₄ represent the number of repeating structural units composed of oxyethylene groups, and n ₁ , n ₂ , n ₃ and n ₄ represent the number of repeating structural units composed of oxypropylene groups. , The total number of repeating oxyethylene groups m ₁ + m ₂ , m ₃ and m ₄ each independently represents an integer of 1 to 30, and the total number of repeating oxypropylene groups n ₁ , n ₂ + n ₃ and n ₄ are independent of each other. Represents an integer of 1 to 30.

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

The total number of repeating oxypropylene groups n ₁ , n ₂ + n ₃ and n ₄ are each independently an integer of 1 to 30, preferably an integer of 5 to 20, and preferably an integer of 8 to 16. Is more preferable and it is still more preferable that it is an integer of 10-14. In terms of excellent resolution improvement and sludge reduction, the total number of repetitions is preferably 20 or less, more preferably 16 or less, and even more preferably 14 or less.

As a compound represented by the general formula (5), R = methyl group, m ₁ + m ₂ = 6 (average value), n ₁ = 12 (average value) vinyl compound (manufactured by Hitachi Chemical Co., Ltd., Trade name: FA-023M). As the compound represented by the general formula (6), R = methyl group, m ₃ = 6 (average value), n ₂ + n ₃ = 12 (average value) vinyl compound (manufactured by Hitachi Chemical Co., Ltd., Product name: FA-024M). As a compound represented by the above general formula (7), a vinyl compound (made by Shin-Nakamura Chemical Co., Ltd., sample) having R = hydrogen atom, m ₄ = 1 (average value), and n ₄ = 9 (average value) Name: NK ester HEMA-9P).

Component (B3): Compound having one ethylenically unsaturated bond in the molecule (B3) Component is not particularly limited, but includes a compound represented by the following general formula (8) in terms of excellent resolution. It is preferable.

［式（８）中、Ｒ^３は水素原子又はメチル基を示し、Ｒ^４は水素原子、メチル基又はハロゲン化メチル基のいずれかを示し、Ｒ^５は炭素数１〜６のアルキル基、ハロゲン原子、水酸基のいずれかを示し、ｐは０〜４の整数を示す。なお、ｐが２以上の場合、複数存在するＲ^５は同一でも異なっていてもよい。−（Ｏ−Ａ）−はオキシエチレン基及び／又はオキシプロピレン基を示し、−（Ｏ−Ａ）−の繰り返し総数ａは１〜４の整数を示す。］

[In the formula (8), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, a methyl group or a halogenated methyl group, and R ⁵ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom. It represents either an atom or a hydroxyl group, and p represents an integer of 0 to 4. When p is 2 or more, a plurality of R ⁵ may be the same or different. -(OA)-represents an oxyethylene group and / or an oxypropylene group, and the total number a of-(OA)-represents an integer of 1 to 4. ]

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

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

  Content of (B) component in the photosensitive resin composition is 30-60 mass with respect to 100 mass parts of total amounts of (A) component and (B) component from a viewpoint of resolution, adhesiveness, and film-forming property. It is preferable to set it as the range of part, and it is more preferable to set it as 40-55 mass parts.

  By the way, the crosslinking density of the cured product of the photosensitive resin composition can be adjusted mainly by a combination of the above-described component (A) and component (B). After adjusting these and photocuring the photosensitive resin composition, the elongation rate at 25 ° C. of the sheet-like cured product having a width of 10 mm and a thickness of 45 μm heated at 120 ° C. for 1 hour in air is 40%. By adjusting as described above, it becomes possible to follow the elongation at the time of bending of the image display device without damaging the partition wall, and it is possible to sufficiently suppress the damage to the partition wall. 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 that can sufficiently suppress the occurrence of breakage.

Component (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 the exposure machine to be used. Specifically, for example, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2 -Aromatic ketones such as dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 2-ethylanthraquinone, Phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2, -Benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, Quinones such as 2,3-dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; 1- (4-methoxyphenyl) -2 , 2-Dimethoxy-2-phenylethane-1-one, 1- (4-methoxyphenyl) -2-methoxy-2-ethoxy-2-phenylethane-1-one, 1- (4-methoxyphenyl) -2 -Methoxy-2-pro Benzyl derivatives such as benzyl ketals such as xyl-2-phenylethane-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one (commonly called benzyldimethyl ketal); 9-phenylacridine, 1,7 -Acridine derivatives such as bis (9,9'-acridinyl) heptane; N-phenylglycine, N-phenylglycine derivatives; coumarin compounds; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2 -(O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4 , 5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Imidazole dimer and the like; and the like. In addition, the substituents of the aryl groups of two 2,4,5-triarylimidazoles in the 2,4,5-triarylimidazole dimer may give the same and symmetrical compounds, or differently asymmetric Such compounds may be provided. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. These can 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 terms of excellent curability at the bottom of the resist after curing of the photosensitive resin composition, and the resist after curing of the photosensitive resin composition. In view of excellent curability at the top, it is preferable to include an acridine derivative, and from the viewpoint of excellent curability in the upper bottom, it is preferable to include both a benzyl derivative such as benzyl ketal and an acridine derivative. In particular, as the thickness of the layer made of the photosensitive resin composition increases, it is necessary to adjust the curability at the bottom of the resist and the curability at the top of the resist in a balanced manner.

  Among them, the component (C) preferably contains an acridine derivative and a benzyl derivative in terms of improving resolution and suppressing the bottoming of the resist after curing, and in particular, 1,7-bis (9,9′-acridinyl). It is preferred to include both) heptane and 2,2-dimethoxy-1,2-diphenylethane-1-one.

  The content of the component (C) in the photosensitive resin composition is 0.1 parts by mass or more in terms of excellent photosensitivity with respect to 100 parts by mass of the total amount of the components (A) and (B). Preferably, it is 0.2 parts by mass or more. In addition, with respect to 100 parts by mass of the total amount of the component (A) and the component (B), it is preferably 20 parts by mass or less, and preferably 10 parts by mass or less in terms of excellent photocurability inside the photosensitive resin composition. It is more preferable that

  In particular, when 1,7-bis (9,9′-acridinyl) heptane is included as the component (C), the content thereof is 100 parts by mass with respect to the total amount of the components (A) and (B). In terms of excellent photosensitivity, 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-diphenylethane-1-one is included as the component (C), the content is 100 parts by mass of the total of the components (A) and (B). On the other hand, 1 mass part or more is preferable and 2 mass parts or more is more preferable in the point which is excellent in a photosensitivity and adhesiveness. Further, from the viewpoint of suppressing outgassing in the heat treatment step, it is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

Component (D): Compound having an epoxy group in the molecule Examples of the component (D) that can be used 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 A type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F type epoxy resins such as bisphenol F diglycidyl ether, and bisphenol S type epoxy such as bisphenol S diglycidyl ether. Resin, biphenol type epoxy resin such as biphenol diglycidyl ether, bixylenol type epoxy resin such as bixylenol diglycidyl ether, hydrogenated bisphenol A type epoxy resin such as hydrogenated bisphenol A glycidyl ether, dicyclopentadiene type epoxy resin, cresol Examples thereof include novolak type epoxy resins and dibasic acid-modified diglycidyl ether type epoxy resins.

  Commercial products can be used as these compounds. For example, as bisphenol A diglycidyl ether, Epicoat 828, Epicoat 1001 and Epicoat 1002 (all manufactured by Japan Epoxy Resin Co., Ltd., trade name) and Epicron 1055 (DIC Corporation, trade name) can be exemplified. .

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

  Examples of the biphenol diglycidyl ether include YL-6121 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). Examples of the bixylenol diglycidyl ether include YX-4000 (product manufactured by Japan Epoxy Resin Co., Ltd., product). Name).

  Furthermore, examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (both manufactured by Tohto Kasei Co., Ltd., trade names), and the dicyclopentadiene type epoxy resin includes Epicron HP-7200L. (Trade name) manufactured by DIC Corporation, and the like. Examples of the cresol novolac type epoxy resin include Epicron N-665-EXP and Epicron N-670-EXP-S (trade name, manufactured by DIC Corporation). Can be mentioned. Examples of the dibasic acid-modified diglycidyl ether type epoxy resin include ST-5100 and ST-5080 (both manufactured by Tohto Kasei Co., Ltd., trade names).

  Among these, dicyclopentadiene type epoxy resin and cresol novolak type epoxy resin are preferable, and cresol novolak type epoxy resin is more preferable in terms of suppressing dissolution of the electrode. Moreover, the 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 in terms of suppressing dissolution of the electrode with respect to 100 parts by mass of the total amount of the components (A) and (B). More than mass part is more preferable. Moreover, in the point which the photosensitive resin composition is excellent in film forming property, 30 mass parts or less are preferable, and 20 mass parts or less are more preferable.

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, which have good light transmittance at wavelengths of 360 nm and 405 nm. In this respect, titanium black is preferable.

  The content of the component (E) in the photosensitive resin composition is preferably 0.1 parts by mass or more in terms of excellent light shielding properties with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferably 2 parts by mass or more. Moreover, 10 mass parts or less are preferable at the point which is excellent in adhesiveness and resolution, and 5 mass parts or less are more preferable.

  The photosensitive resin composition containing the components as described above may further comprise a dye such as malachite green, a photochromic agent such as tribromophenyl sulfone or leuco crystal violet, a thermal color developing inhibitor, p-toluenesulfonamide, if necessary. Plasticizers such as, pigments other than black, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. About 0.01-20 mass parts can each be contained with respect to 100 mass parts of total amounts of (A) component and (B) component. These can be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention containing the components as described above can be obtained, for example, by uniformly kneading and mixing the contained components with a roll mill, a bead mill or the like. If necessary, it can 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 to obtain a solid content of 30 It can be used as a solution of about ˜60% by mass.

  A method for forming a photosensitive resin composition layer on a substrate for an image display device using the obtained photosensitive resin composition is not particularly limited, but the photosensitive resin composition is used as a liquid resist on the substrate. A method of applying and drying can be used. Moreover, a protective film can be coat | covered on the photosensitive resin composition layer as needed. Further, as will be described in detail later, it is preferable to use the photosensitive resin composition layer in the form of a photosensitive element. Examples of the protective film used as a liquid resist and coated with a protective film after coating include polymer films such as polyethylene and polypropylene.

  The photosensitive resin composition was obtained by photo-curing the photosensitive resin composition and then heating at 120 ° C. for 1 hour in air for 1 hour in width and 45 μm thick sheet-like cured product at 25 ° C. Is 40% or more. This elongation percentage is 40% or more and more preferably 60% or more from the viewpoint of suppressing breakage during bending. The elongation percentage of the cured product can be adjusted by reducing the crosslinking density of the cured product by a combination of the component (A) and the component (B).

  Here, photocuring of the photosensitive resin composition is carried out by exposing with a necessary energy amount when forming the partition using the photosensitive resin composition, and developing as necessary. The amount of energy is preferably an amount of energy at which the number of remaining step stages after development of the 41-step step tablet is 29.0.

As a specific method for measuring the elongation rate of the cured product, the cured product is formed into a sheet having a width of 10 mm and a thickness of 45 μm, and the cured product is obtained at a constant speed of 25 ° C., a distance between chucks of 50 mm, and a speed of 2 cm / min. The method of obtaining the elongation percentage (%) when pulled until it breaks by the following formula is used.
Elongation rate (%) = {(length at break-initial length) / initial length} × 100

  Further, the photosensitive resin composition is formed by forming a photosensitive resin composition layer composed of the photosensitive resin composition on a transparent electrode, photocuring the photosensitive resin composition layer, and then at 120 ° C. in air. It is preferable that the wire is not disconnected when a direct voltage of 80 V is applied to the transparent electrode for 100 hours under conditions of 60 ° C. and 90% RH after heating for 1 hour.

  Here, the photocuring of the photosensitive resin composition layer is carried out by exposing the photosensitive resin composition layer with an energy amount necessary for forming a partition using the photosensitive resin composition layer, and developing as necessary. The amount of energy is preferably an amount of energy at which the number of remaining step stages after development of the 41-step 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 with a tester, and those that can be measured are regarded as having no disconnection due to dissolution, and those that are not measurable are determined as having disconnection due to dissolution. For those that can be measured, the rate of increase from the initial resistance value can also be obtained.

(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 made of the photosensitive resin composition formed thereon, and a photosensitive resin composition layer. Protective film 3 formed on 2. In addition, the protective film 3 is provided as needed.

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

  Although the formation method of the photosensitive resin composition layer 2 on the support body 1 is not specifically limited, It can implement preferably by apply | coating and drying the solution of the photosensitive resin composition. Although the thickness of the photosensitive resin composition layer to be applied varies depending on the required properties, the thickness after drying is preferably about 10 to 100 μm, more preferably 20 to 100 μm, and more preferably 30 to 100 μm. Is more preferable, and it is especially preferable that it is 40-100 micrometers.

  The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater. Drying can be performed, for example, at 70 to 150 ° C. for about 2 to 30 minutes. Moreover, it is preferable that the amount of the residual organic solvent in the photosensitive resin composition layer 2 shall be 2 mass% or less from the point which prevents the spreading | diffusion of the organic solvent in a next process.

  A 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. The protective film 3 has a smaller adhesive force between the photosensitive resin composition layer 2 and the protective film 3 than the adhesive force between the photosensitive resin composition layer 2 and the support 1. Preferably, an olefin film such as polyethylene or polypropylene or a polyester film typified by polyethylene terephthalate is used. When a polyester film is used as the support 1 and the same kind of polyester film is used for the protective film 3, it is preferable to use a protective film 3 whose surface is in contact with the photosensitive resin composition layer.

  Further, these protective films 3 are preferably low fisheye films. Here, “fish eye” means that foreign materials, undissolved materials, oxidatively deteriorated materials, etc. of the material are contained in the film when the material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.

  Furthermore, the photosensitive element 10 has an intermediate layer and a protective layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer in addition to the photosensitive resin composition layer 2, the support 1 and the optional protective film 3. You may do it.

  The manufactured photosensitive element 10 is usually wound around a cylindrical core and stored. At this time, it is preferable that the support 1 is wound up so as to be on the outside. An end face separator is preferably installed on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. The term “edge fusion” as used herein refers to a phenomenon in which the photosensitive resin composition layer 2 oozes out from the end face, which is also called cold flow. When this phenomenon occurs, it becomes a foreign matter generation source when forming the partition wall, which is an undesirable phenomenon. Further, as a packing method, it is preferable to wrap and package in a black sheet having small moisture permeability and excellent light shielding properties. Examples of the material of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer).

(Method for forming partition of image display device, method for manufacturing image display device, and image display device)
Next, a method for forming a partition of an image display device using the photosensitive resin composition or photosensitive element of the present invention, a method for manufacturing the image display device, and an image display device will be described.

  First, as shown in FIG. 2A, an electrode substrate 30 comprising an electrode 4 and a substrate 5 is prepared. As shown in FIG. 2B, the above-described photosensitive element 10 is formed on the electrode substrate 30. The photosensitive resin composition layer 2 and the support 1 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 a flexible electrode 4 such as ITO, IZO, and Ag wire ink is formed. Examples of the method of forming the electrode 4 include a method of patterning an electrode material laminated by a method such as vapor deposition and sputtering using a photolithography method, a method of patterning a photosensitive electrode material, and the like. There are no particular restrictions on the method of forming this electrode 4.

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

In the lamination method using the photosensitive element 10, when the protective film 3 is present on the photosensitive resin composition layer 2, the photosensitive element 10 is laminated on the electrode substrate 30 while removing the protective film 3. As the lamination condition, for example, the photosensitive resin composition layer 2 is pressed onto the electrode substrate 30 with a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ) while heating to about 70 to 130 ° C. The method of laminating by doing, etc. are mentioned, It is also possible to laminate | stack under reduced pressure. The surface of the electrode substrate 30 is usually formed with an electrode pattern, but may be flat or 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 an actinic ray 8 in the form of an image, and the exposed portion is photocured (exposure process). . As a method of irradiating the actinic light 8 in an image form, as shown in FIG. 2B, a mask pattern 7 is placed on the photosensitive resin composition layer 2 and the actinic ray 8 is irradiated in an image form for exposure. There is a method of photocuring a part of the photosensitive resin composition layer 2. The mask pattern 7 may be a negative type or a positive type, and those generally used can be used. As the light source of the actinic ray 8, a known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used. As an exposure method, a direct drawing exposure method in which a pattern is directly drawn with a laser without using the mask pattern 7 can also be used.

  After the exposure, as shown in FIG. 2 (c), the photosensitive resin composition layer 2 in the unexposed area is selectively removed by development to be photocured on the substrate for the image display device (electrode substrate 30). An object pattern 20 is formed (development process). In the development step, when the support 1 is present, the support 1 is removed prior to development.

  Development is performed by removing unexposed portions by wet development, dry development, or the like using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. In the present invention, it is preferable to use an alkaline aqueous solution. Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5 mass% sodium carbonate, a dilute solution of 0.1 to 5 mass% potassium carbonate, a dilute solution of 0.1 to 5 mass% potassium hydroxide, and the like. . 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. Moreover, you may mix surfactant, an antifoamer, an organic solvent, etc. in alkaline aqueous solution. Examples of the development method include a dip method, a spray method, brushing, and slapping. The spray method is preferable for improving the resolution.

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

  Further, a step of filling a display medium such as particles in the photocured product pattern 20 formed in the above step, a step of attaching another electrode substrate 30 to the photocured product pattern 20 ((d) and ( Through e)) and the like, the formation of the partition of the image display device and the manufacture of the image display device can be completed.

  The step of attaching another electrode substrate 30 to the photocured material pattern 20 can be performed as follows. That is, in the above process, the adhesive 40 is laminated on the photocured material pattern 20 as shown in FIG. 2D, and the electrode substrate 30 and the photocured material are cured by the adhesive 40 as shown in FIG. This is done by adhering the object pattern 20. A transparent electrode substrate is used at least for the electrode substrate on the display surface side of the image display device.

  The image display device formed through the above-described steps includes an electrode substrate 30 having flexibility and a partition made of a photocured material pattern 20 having high elongation, and achieves excellent flexibility. Can do. In particular, depending on the selection of the material of the electrode 4, an image display device having a high degree of flexibility capable of dealing with a curvature radius of about 5 to 15 mm can be obtained. Moreover, the partition formed using the photosensitive resin composition of the present invention can sufficiently suppress the occurrence of breakage even when the image display device is bent with a curvature radius of about 5 to 15 mm.

  Hereinafter, the present invention will be described more specifically 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 1-4 and Comparative Examples 1-5)
After blending 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 and dissolved therein. The photosensitive resin composition of Examples 1-4 and Comparative Examples 1-5 was obtained. The amount of each component (unit: g) is as shown in Table 1.

The details of each component in Table 1 are as follows. In addition, about (A) component, although the following quantity was mix | blended as a resin solution, in Table 1, the quantity of solid content was shown.
(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 93.75 g (solid content 45 g)
* 2: 48% by mass of methyl cellosolve / toluene (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) Ratio 6/4) 93.75 g of solution (solid content 45 g)

(B) component: photopolymerizable compound * 3; a photopolymerizable compound obtained by reacting a hydroxyl group-terminated polycarbonate compound, organic isocyanate and 2-hydroxyethyl acrylate (weight average molecular weight 4000, Hitachi Chemical Co., Ltd.) (Product name: HT-9082-95)
* 4; UA-21EB (made by Shin-Nakamura Chemical Co., Ltd., trade name)
* 5; FA-023M (trade name, manufactured by Hitachi Chemical Co., Ltd.)
* 6; FA-024M (trade name, manufactured by Hitachi Chemical Co., Ltd.)
* 7; γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-MECH)

Component (C): Photopolymerization initiator * 8; N, N′-tetraethyl-4,4′-diaminobenzophenone (Hodogaya Chemical Co., Ltd., trade name: EAB)
* 9; Tribromomethylphenylsulfone (manufactured by Sumitomo Seika Co., Ltd., product name: TPS)
* 10; 1,7-bis (9-acridinyl) heptane (manufactured by ADEKA Corporation, trade name: N-1717)
* 11; benzyl dimethyl ketal (Ciba Specialty Chemicals, trade name: I-651)

Component (D): Compound having an epoxy group in the molecule * 12; Cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name: EPICLON N-670-EXP-S)
* 13: Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, trade name: EPICLON HP-7200L)
* 14: Bisphenol A type epoxy resin (manufactured by DIC Corporation, trade name: EPICLON 1055)
* 15: Cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name: EPICLON N-665-EXP)

Block isocyanate compound * 16; Block isocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name: Sumidur BL3175)
* 17: Block isocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name: Death Module BL3475)
* 18: Block isocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name: Death Module VPLS2253)

(E) component: inorganic black pigment * 19; titanium black dispersion (manufactured by Gemco, trade name: BT-1HCA)

Other components * 20; pigment dispersant (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Floren DOPA-17HF)
* 21; methacryloyloxypropyltrimethoxysilane (manufactured by Dow Corning Toray, trade name: SZ-6030)

  Next, the obtained photosensitive resin composition solution was uniformly applied onto a 16 μm-thick polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name: HTR-02), and hot air convection drying at 90 ° C. The photosensitive resin composition layer was formed by drying with a machine for 10 minutes. Then, the photosensitive resin composition layer was protected with a polyethylene protective film (tensile strength in the film longitudinal direction: 16 MPa, tensile strength in the film width direction: 12 MPa, manufactured by Tamapoly Co., Ltd., trade name: NF-15). A photosensitive element was obtained. The film thickness after drying of the photosensitive resin composition layer was 45 μm.

  On the ITO surface of a PET substrate with ITO (trade name: R-300, manufactured by Toyobo Co., Ltd.), the photosensitive element is polyethylene so that the photosensitive resin composition layer is in contact with the surface of the PET substrate with ITO. The film was laminated through a laminating roll heated to 110 ° C. while peeling off the protective film. From the bottom, the structure of the obtained laminate is a PET substrate with ITO, a photosensitive resin composition layer, and a polyethylene terephthalate film. The obtained laminate was evaluated for sensitivity, adhesion, resolution, and goby folding.

<Evaluation of sensitivity>
Using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp, a phototool having a 41-step tablet was brought into close contact with the laminated polyethylene terephthalate film for exposure. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer. The energy amount (exposure amount) at which the number of remaining step steps after development of the 41-step tablet was 29.0 was defined as sensitivity (mJ / cm ² ). It shows that a sensitivity is so high that the numerical value of this energy amount is small. Table 2 shows the evaluation results. Table 2 shows the actual number of remaining steps when exposure is performed with the above energy amount.

<Evaluation of adhesion>
Using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp, the line width / space width is 10/300 to 80/300 (unit: μm, space width constant as a negative for adhesion evaluation) ) And a photo tool having a 41-step tablet are closely attached to the polyethylene terephthalate film of the laminate, and the amount of remaining energy after developing the 41-step tablet is 29.0. The exposure was performed. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer and evaluate the adhesion. Adhesion is represented by the width (μm) of the smallest line that remains without being peeled off by the developer. The smaller the value, the tighter the line is, without peeling from the glass substrate. Is high. Table 2 shows the evaluation results.

<Evaluation of resolution>
A phototool having a 41-step tablet and a phototool having a wiring pattern having a line width / space width of 30/30 to 200/200 (unit: μm) as a resolution evaluation negative on a polyethylene terephthalate film of a laminate Using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp lamp, the exposure was performed with an energy amount of 29.0 after the development of the 41-step tablet. . After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass sodium carbonate aqueous solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer and evaluate the resolution. The resolution is represented by the smallest space width (μm) in which the unexposed portion is removed favorably by the development processing, and the smaller the numerical value, the better the resolution.
Table 2 shows the evaluation results.

<Goat folding test>
Using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp, exposure was performed with an energy amount such that the number of remaining step stages after development of the 41-step step tablet was 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer. Subsequently, it was left still for 1 hour in the box-type dryer (Mitsubishi Electric Corporation make, model number: NV50-CA, air atmosphere) heated to 120 degreeC. The evaluation sheet thus obtained is folded, and the cured product of the photosensitive resin composition layer is not peeled off from the PET substrate with ITO, and no damage is seen, and the peeling is seen from the PET substrate with ITO, Alternatively, B was determined to be damaged.

<Solubility of electrode>
On the IZO and ITO surfaces of an IZO-TEG (Test Element Group) substrate and an ITO-TEG (Test Element Group) substrate, the photosensitive element is composed of an IZO-TEG substrate and an ITO-TEG substrate, respectively. The film was laminated through a laminating roll heated to 110 ° C. while peeling off the polyethylene protective film so as to be in contact with the surface. The structure of the obtained laminate is a TEG substrate, a photosensitive resin composition layer, and a polyethylene terephthalate film from the bottom. A phototool having a 41-step tablet is adhered onto a polyethylene terephthalate film of a laminate, and a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp lamp is used to determine the number of remaining steps after development. Exposure was performed with an energy amount of 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer. Thereby, the evaluation board | substrate with which the photocured material of the photosensitive resin composition layer was formed on the TEG board | substrate was obtained. Subsequently, the obtained evaluation board | substrate was left still for 1 hour in the box-type dryer (the Mitsubishi Electric Corporation make, model number: NV50-CA) heated at 120 degreeC. Thereafter, under the conditions of 60 ° C. and 90% RH, a DC voltage of 80 V was applied to the electrode 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 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 impossible to measure and it is determined that there is disconnection due to dissolution. As for A, a value obtained by dividing the resistance value of the anode after 100 hours by the initial resistance value and multiplying by 100 is indicated as a rate of increase in resistance (%). It can be evaluated that dissolution of the electrode is suppressed as the resistance increase rate is smaller.

<Elongation of cured product>
The photosensitive element is placed on a polytetrafluoroethylene sheet (manufactured by Nitto Denko Corporation, product name: Nitoflon Film No. 900U), so that the photosensitive resin composition layer is in contact with the surface of the polytetrafluoroethylene sheet. The film was laminated through a laminating roll heated to 110 ° C. while peeling off the polyethylene protective film. The structure of the obtained laminate is in the order of a polytetrafluoroethylene sheet, a photosensitive resin composition layer, and a polyethylene terephthalate film. It exposed using the parallel light exposure machine EXM-1201 (made by Oak Manufacturing Co., Ltd.) on the polyethylene terephthalate film of the said laminated body. In the exposure of the laminate, the energy amount was such that the number of remaining step steps after development of the 41-step tablet was 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 30 seconds to remove the unexposed portion of the photosensitive resin composition layer. Thereby, the evaluation sheet | seat in which the photocured material of the photosensitive resin composition layer was formed on the polytetrafluoroethylene sheet was obtained. Subsequently, the obtained evaluation sheet was allowed to stand for 1 hour in a box-type dryer (Mitsubishi Electric Corporation, model number: NV50-CA, air atmosphere) heated to 120 ° C. The evaluation sheet after the heat treatment was cut into a width of 10 mm, the distance between chucks was set to 50 mm, and the cured product of the photosensitive resin composition layer was pulled at a constant speed of 2 cm / min until the cured product of the photosensitive resin composition was broken. Elongation rate (%) was determined. Table 2 shows the evaluation results.

  As is clear from the results shown in Table 2, it was confirmed that the presence of the component (D) suppresses dissolution of the electrode. As for the elongation, it was confirmed that a high degree of elongation of 40% or more can be obtained, and that the breakage of the partition walls during bending can be suppressed.

  As described above, according to the present invention, a photosensitive film capable of forming a partition for an image display device capable of suppressing breakage during bending while suppressing dissolution of an electrode when a voltage is applied under high temperature and high humidity. A photosensitive resin composition, a photosensitive element using the same, a method for forming partition walls of an image display device, a method for manufacturing an image display device, and an image display device can be provided.

DESCRIPTION OF SYMBOLS 1 ... Support body, 2 ... Photosensitive resin composition layer, 3 ... Protective film, 4 ... Electrode, 5 ... Substrate, 10 ... Photosensitive element, 20 ... Hardened | cured material (photocured material pattern) of the photosensitive resin composition, 30 ... Electrode substrate, 40 ... Adhesive.

Claims (9)

A photosensitive resin composition for forming a partition separating pixels in a flexible image display device having a transparent electrode on at least a display surface,
The photosensitive resin composition is
(A) component: a binder polymer having a carboxyl group in the molecule;
(B) component: a photopolymerizable compound,
Component (C): a photopolymerization initiator, and
(D) component: a compound having an epoxy group in the molecule,
Containing
The photosensitive resin composition is photocured and then heated at 120 ° C. for 1 hour in air, and the sheet-like cured product having a width of 10 mm and a thickness of 45 μm has an elongation at 40 ° C. of 40% or more. Photosensitive resin composition.   Furthermore, (E) component: The photosensitive resin composition of Claim 1 containing an inorganic type black pigment.   The photosensitive resin composition of Claim 2 in which the said (E) component contains titanium black.   A photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition as described in any one of Claims 1-3 formed on this support body. 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 for separating pixels.
A laminating step of laminating a photosensitive resin composition layer made of the photosensitive resin composition according to any one of claims 1 to 3 on a substrate of the image display device;
An exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photocure an exposed portion; and
A development step of removing a portion other than the exposed portion of the photosensitive resin composition layer to form a photocured product pattern;
A method for forming a partition wall of an image display device. A method of manufacturing an image display device having flexibility, comprising at least a transparent electrode disposed on a display surface and a partition wall for separating pixels,
A method for manufacturing an image display device, comprising the step of forming the partition wall by the method according to claim 5.   The method for manufacturing an image display device according to claim 6, wherein the transparent electrode is made of a material formed by applying a solution containing at least one type of metal conductive fiber. Filling the partition with a display medium;
A step of attaching the substrate to the opposite side of the partition so as to face one of the substrates;
The manufacturing method of the image display apparatus of Claim 6 or 7 further including these. The image display apparatus manufactured by the manufacturing method as described in any one of Claims 6-8.

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