TWI509357B - A photosensitive resin composition, a photosensitive member using the same, a partition wall forming method of an image display device, a method of manufacturing an image display device, and an image display device - Google Patents

Description

Photosensitive resin composition, photosensitive element using the same, partition wall forming method of image display device, method of manufacturing image display device, and image display device

The present invention relates to a photosensitive resin composition, a photosensitive element using the composition, 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.

In recent years, an image display device (PLD: Paper Like Dispaly) which is as thin as paper, portable, and capable of displaying characters or images has been attracting attention. Such an image display device has the advantages of paper as a general printed matter, such as visibility and portability. Further, since the information can be re-entered electronically, it is also considered as a paper substitute for environmental protection or cost considerations. And practical.

As a display technique of an image display device, various types such as a pattern for moving particles by electrophoresis or the like, a liquid crystal type, and an electrochemical type have been proposed (for example, refer to Non-Patent Document 1). In particular, as a mode for moving particles, methods such as a microcapsule electrophoresis method, a microcup type electrophoresis method, an electronic powder fluid method, and a toner display method have been studied. These methods enclose a white and black particle as a display medium between transparent electrodes, and apply an electric field, which is displayed by electrically moving the particles to form a white/black image. Further, the driving method of the image display device is active driving and passive driving, and the back surface technology (panel circuit) for the image display device has also been studied.

In the case of the particle moving type image display device described above, it is necessary to use a partition wall in which white/black particles are sealed as described above. As the partition wall In the formation method, 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, refer to Patent Document 1). Among them, a photolithography method in which a photosensitive resin composition is used and a high-definition pattern can be efficiently formed by irradiation with active rays is attracting attention.

Recently, there have been reports to study the flexibility of an image display device or to display a color filter by a white/black image display to realize full-color display (for example, refer to Non-Patent Document 2).

When the flexibility of the image display device is performed, the flexibility of the electrode substrate is necessary. Since ITO (Indium Tin Oxide) used as a transparent electrode has a lack of flexibility, IZO (Indium Zinc Oxide) and Ag wires have been studied in recent years. An ITO substitute such as an ink or an organic conductive material (for example, refer to Non-Patent Document 3). Regarding the degree of flexibility, various studies have been conducted from the degree of being able to be deflected to the extent that the volume can be reduced and the volume is reduced when carried. Regarding the radius of curvature of a small group, it is generally assumed that the bending limit of the ITO electrode substrate is about 15 to 20 mm, but the Ag wire. Inks, organic conductive materials, and combinations thereof can reduce the radius of curvature to about 5 to 15 mm.

Further, when the full color display is performed, since the image display device for white/black display uses a color filter in combination, it is necessary to increase the contrast between the pixels. Therefore, it is necessary to use a light shielding layer that shields light between pixels. In the case of monochrome display, color filters are not used, and in order to improve the image brightness of the image display device, transparency is required instead of light blocking.

The partition wall of the image display device using the photolithography method is formed as follows. That is, a method comprising the steps of: a photolithography technique for laminating a light-shielding layer called a black matrix; further comprising the step of forming a photosensitive resin composition layer by coating a photosensitive resin composition on the light-shielding layer or laminating a photosensitive element; a step of irradiating a specific portion of the photosensitive resin composition layer with active light rays to photoharden the exposed portion, and removing the unexposed portion to form a photocured pattern. Further, a light shielding layer called a black matrix may be omitted. Therefore, sensitivity, resolution, and adhesion to a substrate are generally required for a photosensitive resin composition for forming a partition wall of an image display device.

Further, in the production of the image display device, the method further comprises the steps of: filling the display medium such as particles in the photo-cured material pattern obtained by the above step, heat-treating the photo-cured pattern, and adhering the electrode; The steps of the substrate, etc. Thereby, an image display apparatus using a cured product of the photosensitive resin composition layer as a partition wall can be obtained.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Publication No. 2007-178881

Non-patent literature

Non-Patent Document 1: Suzuki Ming, "The Latest Trend of Electronic Paper 2007", October 10, 1999, Japanese Society of Image Society, Volume 46, No. 5: 372-384 (2007)

Non-Patent Document 2: Tanuma Yafu, "Flexible Electronic Paper Using Electronic Powder Fluid", October 10, 1999, Japan Image Society, Vol. 46, No. 5: 396-400 (2007)

Non-Patent Document 3: Genjin 祯, "Introducing new materials into transparent electrodes , August 10, 2011, Nikkei Electronics 59-65 (2009)

Summary of invention

In the step of adhering the electrode substrate, since a voltage is applied under high temperature and high humidity, the electrode portion which is adhered to the cured product of the photosensitive resin composition may be dissolved. In fact, IZO, which has been studied as a conductive substrate for flexibility, contains amphoteric metal zinc, which causes a problem of dissolution in the step of adhering the electrode substrate. Further, the electrode material has a high degree of flexibility and can correspond to a radius of curvature of about 5 to 15 mm, for example, an Ag wire is used in the electrode material. In the case of inks, organic conductive materials, and combinations thereof, there is a problem that the partition wall material is broken when bent.

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

In order to achieve the above object, the present invention provides a photosensitive resin composition which is a photosensitive resin composition for forming a partition wall separating pixels, which is at least on a display surface, in an image display device. An image display device having a transparent electrode and having flexibility, the above photosensitive resin The 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) component: an epoxy in the molecule In the base compound, after the photoreceptor composition was photocured, it was heated at 120 ° C for 1 hour in air to have a sheet-like cured product having a width of 10 mm and a thickness of 45 μm and an elongation at 25 ° C of 40% or more.

By the photosensitive resin composition having the above-described composition, it is possible to suppress the dissolution of the electrode which causes a problem in forming the partition wall of the image display device, and to form a partition wall capable of suppressing breakage during bending. Moreover, the photocurable material pattern excellent in resolution and adhesion can be formed with good sensitivity by the photosensitive resin composition. The reason why the dissolution of the electrode is suppressed by the photosensitive resin composition of the above composition is not clear. However, it is considered that the component (D) captures the carboxyl group remaining in the cured product of the photosensitive resin composition, thereby suppressing dissolution of the electrode. . Further, it is possible to suppress the cause of breakage of the partition wall during bending, and it is considered that the elongation is adjusted to the above range by lowering the crosslinking density of the cured product of the photosensitive resin composition, so that the partition wall can conform to the image display device. Extends during bending without breaking. According to the photosensitive resin composition of the present invention, it is possible to form a partition wall which can sufficiently suppress the occurrence of breakage even when the image display apparatus is bent at a curvature radius of about 5 to 15 mm.

The photosensitive resin composition of the present invention may further contain (E) a component: an inorganic black pigment. Further, the component (E) preferably contains titanium black. By including such a component (E), the opposite characteristics of light sensitivity and light blocking property can be maintained in a well-balanced manner. On the other hand, in order to increase the brightness of the image display device, it is sometimes necessary to completely exclude the inorganic black pigment (( E) The photosensitive resin composition for forming a partition wall and the photosensitive element using the composition, the component (E) may be added as needed.

The present invention also provides a photosensitive element comprising: a support and a photosensitive resin composition layer formed on the support, wherein the photosensitive resin composition layer is the photosensitive resin composition of the present invention Composition. By using such a photosensitive element, it is possible to suppress dissolution of an electrode which causes a problem in forming a partition wall of an image display device, and to form a partition wall capable of suppressing breakage during bending. Moreover, by such a photosensitive element, a photocured material pattern excellent in resolution and adhesion can be formed with good sensitivity.

The present invention also provides a method of forming a partition wall of an image display device, the image display device comprising an image display device having at least a transparent electrode disposed on a display surface and a partition wall separating pixels, and having flexibility The forming method includes the step of laminating a photosensitive resin composition layer composed of the photosensitive resin composition of the present invention on a substrate of the image display device; and irradiating the active light to the photosensitive resin An exposure step of photohardening the exposed portion of the specific portion of the layer, and a step of removing the portion other than the exposed portion of the photosensitive resin composition layer to form a photocured pattern.

The present invention further provides a method of manufacturing an image display device comprising a transparent electrode disposed on a display surface and a partition wall separating pixels, and a method of manufacturing an image display device having flexibility The manufacturing method has the step of forming the partition wall by the method of forming the partition wall of the image display device of the present invention described above.

According to the method and image display of the partition wall of the above image display device In the method for producing a device, since the partition wall is formed by the photosensitive resin composition of the present invention, it is possible to suppress the dissolution of the electrode when the partition wall is formed, and to form a partition wall capable of suppressing breakage during bending.

In the method of manufacturing an image display device described above, the transparent electrode is preferably made of a material formed by applying a solution containing at least one type of metal conductive fiber. Thereby, an image display device having excellent flexibility comparable to a curvature radius of about 5 to 15 mm can be formed. Moreover, the electrode material can be, for example, an Ag wire. Ink, etc.

Moreover, it is preferable that the method of manufacturing the image display device further includes a step of filling the display medium in the partition wall and a step of adhering the substrate to the opposite side of the partition wall so as to face the substrate on the other side.

The present invention also provides an image display device characterized by being manufactured by the above-described manufacturing method. Since these image display apparatuses are manufactured by the above-described manufacturing method, it is possible to suppress the dissolution of the transparent electrode and to provide a partition wall capable of suppressing breakage during bending, and the reliability of the apparatus is increased.

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

Form for implementing the invention

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding portions are designated by the same reference numerals, and the description thereof will not be repeated. Further, the dimensional ratio of the drawings is not limited to the illustrated ratio. Further, in the present specification, (meth)acrylic acid means acrylic acid and methacrylic acid corresponding thereto, and (meth)acrylic acid ester means acrylate and methacrylate corresponding thereto, (meth)acrylic acid oxime The base means an acryl fluorenyl group and a methacryl oxime group corresponding thereto.

(Photosensitive resin composition)

The photosensitive resin composition of the present invention is a photosensitive resin composition for forming a partition wall for separating pixels in an image display device, and the image display device has a curved shape including a transparent electrode on at least a display surface. In the image display device, the photosensitive resin composition contains the component (A): a binder polymer having a carboxyl group in the molecule, (B) a component: a photopolymerizable compound, (C) component: a photopolymerization initiator, and (D) Component: a compound having an epoxy group in the molecule, and the photosensitive resin composition is photocured, and then heated at 120 ° C for 1 hour in air to form a sheet-like cured product having a width of 10 mm and a thickness of 45 μm at 25 ° C. The rate is 40% or more.

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

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

The component (A) which 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 a film property, and for example, Acrylic resin, styrene resin, epoxy resin, guanamine resin, guanamine epoxy resin, alkyd resin, phenol resin, urethane resin. Among them, from the viewpoint of alkali developability, an acrylic resin is preferred. These resins may be used singly or in combination of two or more. Examples of the combination of two or more kinds of the binder polymers include two or more kinds of binder polymers composed of different copolymerized components, and two or more kinds of binder polymers having different weight average molecular weights. Two or more kinds of binder polymers having different dispersities. Further, a polymer having a complex mode molecular weight distribution described in Japanese Laid-Open Patent Publication No. Hei 11-327137 can also be used. Further, the binder polymer may have a photosensitive group as needed.

The component (A) can be produced, for example, by radically polymerizing a polymerizable monomer having a carboxyl group with another polymerizable monomer. The polymerizable monomer may, for example, be styrene; a polymerizable styrene derivative such as vinyl toluene, α-methylstyrene, p-methylstyrene or p-ethylstyrene; acrylamide; acrylonitrile; Ethyl alcohol esters such as vinyl-n-butyl ether; alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, (meth)acrylic acid Ethylaminoethyl ester, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate Ester, (meth)acrylic acid, α-bromo (meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid, etc. Acrylic acid; maleic acid; maleic acid monoester of maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid, cinnamic acid , α-cyano cinnamic acid, itaconic acid, croton Acid, propionic acid. The polymerizable monomer having a carboxyl group is preferably (meth)acrylic acid from the viewpoint of developability and stability. Further, these monomers may be used singly as a homopolymer or in combination of two or more kinds as a copolymer.

The alkyl (meth)acrylate may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate or amyl (meth)acrylate. And (hexyl) (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the isomers thereof.

The component (A) is preferably an acrylic copolymer containing methacrylic acid, methyl methacrylate, and butyl methacrylate from the viewpoint 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, still more preferably 130 mgKOH/g or more, and particularly preferably 180 mgKOH/g or more. The viewpoint of excellent liquid resistance and adhesion is preferably 250 mgKOH/g or less, preferably 240 mgKOH/g or less, more preferably 230 mgKOH/g or less, and particularly preferably 220 mgKOH/g or less. Further, in the case of developing in a solvent for the development step, it is preferred to suppress the amount of the polymerizable monomer having a carboxyl group to be used.

Here, the acid value can be measured as follows. That is, first, after weighing about 1 g of the resin solution to be measured for the acid value, 30 g of acetone was added to the resin solution, and this was uniformly dissolved. Then, phenolphthalein as an indicator was added to the solution in an appropriate amount, and the measurement was carried out using a 0.1 N aqueous KOH solution. Then, the acid value is calculated according to the following formula.

A=10×Vf×56.1/(Wp×I)

In the formula, A represents an acid value (mg KOH/g), Vf represents a titration (mL) of a 0.1 N aqueous KOH solution, Wp represents a mass (g) of the measured resin solution, and I represents a measured resin solution. The proportion of non-volatile components (% by mass).

The weight average molecular weight of the component (A) (measured by gel permeation chromatography (GPC) and converted by standard polystyrene) is preferably 20,000 or more in terms of excellent liquid resistance. It is preferably 25,000 or more, more preferably 30,000 or more. The viewpoint of shortening the development time is preferably 300,000 or less, preferably 150,000 or less, and more preferably 100,000 or less. Further, the weight average molecular weight of the binder polymer is measured by gel permeation chromatography and converted to a standard polystyrene calibration line. The measurement conditions of gel permeation chromatography (GPC) are as follows.

[GPC measurement conditions]

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

Pipe column: Gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R440 (3 in total) (above, manufactured by Hitachi Chemical Co., Ltd., trade name)

Effervescent solution: tetrahydrofuran

Measuring temperature: 25 ° C

Flow rate: 2.05mL/min

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

The content of the component (A) in the photosensitive resin composition is relative to The total amount of the component (A) and the component (B) is preferably 40 parts by mass or more, preferably 45 parts by mass or more, from the viewpoint of excellent coating property of the photosensitive resin composition. The viewpoint of the mechanical strength of the photocured material is preferably 70 parts by mass or less, preferably 60 parts by mass or less, based on 100 parts by mass of the total of the components (A) and (B).

(B) component: photopolymerizable compound

The component (B) which can be used in the present invention is not particularly limited as long as it can be photocrosslinked, and examples thereof include a component (B1): a compound having an ethylenically unsaturated group and a urethane bond in the molecule, ( Component B2): a compound obtained by reacting a polyhydric alcohol and/or a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, and a component (B3): a compound having one ethylenically unsaturated bond in the 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 of improving the elongation of the cured product and having excellent adhesion to the flexible substrate.

The component (B1) which can be used in the present invention is not particularly limited, but it is preferred to contain a compound having a trimeric isocyanate ring structure. The compound having a trimeric isocyanate ring structure may, for example, be a compound represented by the following formula (1).

In the formula (1), R ¹ each independently represents a group represented by the following formula (2), a group represented by the following formula (3), or a group represented by the following formula (4). At least one of R ¹ is a group represented by the following formula (4)]

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

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

[In the 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 the modulus of elasticity and the adhesion, at least two of R ¹ in the formula (1) are preferably a group represented by the following formula (4), and more preferably all of R ¹ are The group represented by the following formula (4).

In the general formulae (2), (3), and (4), m is preferably an integer of 1 to 6 from the viewpoint of excellent chemical resistance. Further, in the general formula (4), m is preferably an integer of 3 to 6 from the viewpoint of excellent mechanical strength.

For the compound represented by the above formula (1), for example, NK oligomer UA-21EB (New Nakamura Chemical Co., Ltd., trade name, general formula (1), R ¹ is a general formula (4) Compound).

Further, the component (B1) preferably contains a compound which can be obtained by subjecting a urethane compound to a condensation reaction with a compound having a hydroxyl group and an ethylenically unsaturated group, and the urethane compound has a polycarbonate compound and/or a polyester compound. The hydroxy group at the terminal end of the reaction with the isocyanate group of the diisocyanate compound has an isocyanate group at the end of the complex number.

These compounds can be synthesized by a conventional method or a commercially available one. For example, UF-8003M, UF-TCB-50, UF-TC4-55 (above trade name, Kyoeisha Chemical Co., Ltd.), HT 9082-95 (trade name, Hitachi Chemical Industry Co., Ltd.) system).

Further, as the component other than the above (B1), for example, a (meth)acrylic monomer having a hydroxyl group at the β-position and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate Addition reactant of isocyanate compound; EO modified urethane di(meth)acrylate, EO, PO modified urethane di(meth)acrylate. The EO-modified urethane di(meth) acrylate is, for example, manufactured by Shin-Nakamura Chemical Co., Ltd., product name UA-11. Further, examples of the EO and PO-modified urethane di(meth)acrylate include a product name UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd.

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

The component (B2) may, for example, be polyethylene glycol di(meth)acrylate (the number of vinyl groups is 2 to 14) or polypropylene glycol di(meth)acrylate (the number of the propylene groups is 2 to 14) Polyolefin glycol di(meth)acrylate; trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy III a trimethylolpropane (meth) acrylate compound such as methyl acrylate or trimethylolpropane propoxy tri(meth) acrylate; tetramethylol methane tri(meth) acrylate, four a tetramethylol methane (meth) acrylate compound such as hydroxymethyl methane tetra(meth) acrylate; dipentaerythritol such as dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate ( a methyl acrylate compound; bisphenol A dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate, etc. Bisphenol A dioxyethylene di(meth) acrylate; trimethylolpropane triglycidyl ether Acrylate and bisphenol A diglycidyl ether acrylate.

In order to maintain the low elasticity of the cured film and to improve the resolution and the adhesion, the component (B2) preferably contains a polyolefin glycol di(meth)acrylate, preferably contains the following formula ( a compound represented by 5), (6), or (7).

In the above 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 number of repetitions of structural units composed of oxyethylene groups, and n ₁ , n ₂ , n ₃ and n ₄ represent the number of repetitions of structural units composed of oxypropylene groups, The total number of repetitions of oxyethylene groups m ₁ + m ₂ , m ₃ and m ₄ respectively represent an integer from 1 to 30, and the total number of repetitions of oxypropenyl groups n ₁ , n ₂ + n ₃ and n ₄ independently represent 1 to 30 Integer.

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

Further, the total number of repetitions n ₁ , n ₂ + n ₃ and n _{4 of the} oxypropylene groups independently represent an integer of 1 to 30, preferably an integer of 5 to 20, preferably an integer of 8 to 16, more preferably 10 to An integer of 14. The total number of repetitions is preferably 20 or less, preferably 16 or less, and more preferably 14 or less, from the viewpoint of improving the resolution and reducing sludge.

The compound represented by the above formula (5) may, for example, be an ethylene compound having R = methyl group, m ₁ + m ₂ = 6 (average value), and n ₁ = 12 (average value) (Hitachi Chemical Industry Co., Ltd. limited) Company system, trade name: FA-023M). The compound represented by the above formula (6) may, for example, be an ethylene compound having R = methyl group, m ₃ = 6 (average value), and n ₂ + n ₃ = 12 (average value) (Hitachi Chemical Industry Co., Ltd. limited) Company system, trade name: FA-024M). The compound represented by the above formula (7) is, for example, a vinyl compound of R = hydrogen atom, m ₄ =1 (average value), and n ₄ = 9 (average value) (manufactured by Shin-Nakamura Chemical Co., Ltd.) , sample name: NK ester HEMA-9P) and so on.

(B3) component: a compound having an ethylenically unsaturated bond in the molecule

The component (B3) is not particularly limited, but from the viewpoint of excellent resolution, it is preferred to contain a compound represented by the following formula (8).

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, and a hydroxyl group. Either p represents an integer from 0 to 4. Further, when p is 2 or more, the plural R ^{5 present} may be the same or different. -(OA)- represents an oxyethylene group and/or an oxypropylene group, and the total number of repetitions a of -(OA)- represents an integer of 1 to 4. ]

The compound represented by the above formula (8) may, for example, be γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-decanoate or β-hydroxyethyl. -β'-(meth)acryloyloxyethyl-o-decanoate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, of which γ-Chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-decanoate. γ-Chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalic acid ester can be obtained commercially as FA-MECH (manufactured by Hitachi Chemical Co., Ltd., product name).

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

The content of the component (B) in the photosensitive resin composition is preferably 100 parts by mass based on the total amount of the components (A) and (B) from the viewpoints of resolution, adhesion, and film formability. 30 to 60 parts by mass, It is preferably 40 to 55 parts by mass.

The crosslinking density of the cured product of the photosensitive resin composition can be mainly adjusted by a combination of the above components (A) and (B). By adjusting the crosslinking density, the photosensitive resin composition is photocured, and then heated at 120 ° C for 1 hour in air to obtain a sheet-like cured product having a width of 10 mm and a thickness of 45 μm and an elongation at 25 ° C adjusted to 40%. In the above, the partition wall can conform to the extension of the image display device during bending without being damaged, and the damage of the partition wall can be sufficiently suppressed. According to the photosensitive resin composition of the present invention, it is possible to form a partition wall which can sufficiently suppress the occurrence of breakage even when the image display apparatus is bent at a curvature radius of about 5 to 15 mm.

(C) component: photopolymerization initiator

The component (C) which can be used in the present invention is not particularly limited as long as it is in accordance with the wavelength of light of the exposure machine to be used, and specific examples thereof include benzophenone and N,N'-tetramethyl-4. , 4'-diaminobenzophenone (Michlerone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-di Methylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1-[4- An aromatic ketone of (methylthio)phenyl]-2-morpholinyl-acetone-1; 2-ethyl fluorene, phenanthrenequinone, 2-tert-butyl fluorene, octamethyl hydrazine, 1 , 2-benzopyrene, 2,3-benzopyrene, 2-phenylindole, 2,3-diphenylanthracene, 1-chloroindole, 2-methylindole, 1,4 - naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylhydrazine, etc.; benzoin methyl ether, benzoin ethyl ether a benzoin ether compound such as benzoin phenyl ether; benzoin, methyl benzoin, ethyl benzoine, etc. Benzoin compound; 1-(4-methoxyphenyl)-2,2-dimethoxy-2-phenylethan-1-one, 1-(4-methoxyphenyl)-2 -methoxy-2-ethoxy-2-phenylethane-1-one, 1-(4-methoxyphenyl)-2-methoxy-2-propoxy-2-phenyl Benzene such as benzyl-1-ketone or 2,2-dimethoxy-1,2-diphenylethane-1-one (commonly known as benzyl dimethyl ketal) a methyl derivative; an acridine derivative of 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine, N-phenylglycine derivative; Coumarin-based compound; 2-(o-chlorophenyl)-4,5-diphenylimidazolium, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole Monomer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium, 2-( An imidazole couple of p-methoxyphenyl)-4,5-diphenylimidazolium or the like. Further, the substituent of the aryl group of two 2,4,5-triarylimidazoles in the 2,4,5-triarylimidazole couple may be the same to obtain a symmetrical compound, or may be different to obtain a non- Symmetrical compound. Further, a thioxanthone-based compound and a tertiary amine compound may be combined as in the combination of diethyl thioxanthone and dimethylamino benzoic acid. These compounds may be used singly or in combination of two or more.

In the above, the photosensitive resin composition preferably contains a benzyl derivative such as benzyl ketal, and the photosensitive resin composition is excellent in the curability of the photosensitive resin composition at the bottom of the photoresist after curing. From the viewpoint of excellent curability in the upper portion of the photoresist after curing, it is preferable to contain an acridine derivative, and it is preferable to contain a benzyl derivative such as benzyl ketal or acridine from the viewpoint of excellent hardenability in both the upper portion and the bottom portion. Both of the derivatives. In particular, when the film thickness of the layer composed of the photosensitive resin composition is thicker, it is necessary to adjust the light in a well-balanced manner. The hardenability of the bottom and the hardenability of the upper part of the photoresist.

In particular, the component (C) preferably contains an acridine derivative and a benzyl derivative, and particularly preferably contains 1 as long as the resolution is good and the bottom tail of the photoresist after curing is suppressed. , 7-bis(9,9'-acridinyl)heptane and 2,2-dimethoxy-1,2-diphenylethane-1-one.

The content of the component (C) in the photosensitive resin composition is preferably 0.1 part by mass or more from the viewpoint of excellent light sensitivity with respect to 100 parts by mass of the total of the components (A) and (B). Preferably, it is 0.2 parts by mass or more. In addition, it is preferably 20 parts by mass or less, and preferably 10 parts by mass, from the viewpoint of being excellent in photocurability in the photosensitive resin composition, with respect to 100 parts by mass of the total of the components (A) and (B). the following.

Wherein, in the case of the above component (C), when 1,7-bis(9,9'-acridinyl)heptane is contained, the content thereof is 100% relative to the total amount of the above components (A) and (B). The mass portion is preferably 0.05 to 1 part by mass, and more preferably 0.1 to 0.5 part by mass, from the viewpoint of excellent light sensitivity.

Further, in the case of the above component (C), when 2,2-dimethoxy-1,2-diphenylethane-1-one is contained, the content thereof is relative to the above component (A) and (B) The total amount of the components is preferably 1 part by mass or more, and preferably 2 parts by mass or more from the viewpoint of excellent light sensitivity and adhesion. Moreover, from the viewpoint of suppressing gas release at the step of heat treatment, it is preferably 10 parts by mass or less, preferably 5 parts by mass or less.

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

As the component (D) which can be used in the present invention, for example, in the molecule A compound having an epoxy group (oxirane ring).

The compound having an epoxy group in the molecule may, for example, be a bisphenol A epoxy resin such as bisphenol A diglycidyl ether or a bisphenol F epoxy resin such as bisphenol F diglycidyl ether. Bisphenol type epoxy resin such as bisphenol S diglycidyl ether, bisphenol type epoxy resin such as bisphenol diglycidyl ether, or bisphenol type such as bisphenol diglycidyl ether Hydrogenated bisphenol A type epoxy resin such as epoxy resin, hydrogenated bisphenol A glycidyl ether, dicyclopentadiene type epoxy resin, cresol novolak type epoxy resin, and dibasic acid of these compounds Modified diglycidyl ether type epoxy resin.

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

Examples of the bisphenol F diglycidyl ether include Epikote 807 (manufactured by Japan Epoxy Resin Co., Ltd., trade name), and bisphenol S diglycidyl ether, for example, EBPS-200 (manufactured by Nippon Kayaku Co., Ltd., a product) Name), and Epichlon EXA-1514 (made by DIC Corporation, trade name).

Further, the bisphenol diglycidyl ether may, for example, be YL-6121 (manufactured by Japan Epoxy Resin Co., Ltd., trade name), and the bisphenol diglycidyl ether may, for example, be YX-4000 (Japan Epoxy Resin Co., Ltd.). System, product name).

Further, examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (all manufactured by Tohto Kasei Co., Ltd., trade names), and the like. The dicyclopentadiene type epoxy resin may, for example, be Epichlon HP-7200L (trade name, manufactured by DIC Corporation), and the cresol novolac type epoxy resin may, for example, be Epichlon N-665-EXP or Epichlon N- 670-EXP-S (made by DIC Corporation, trade name). In addition, the above-mentioned dibasic acid-modified diglycidyl ether type epoxy resin may, for example, be ST-5100 or ST-5080 (all manufactured by Tohto Kasei Co., Ltd., trade name).

Among these, from the viewpoint of suppressing dissolution of the electrode, a dicyclopentadiene type epoxy resin and a cresol novolak type epoxy resin are preferable, and a cresol novolak type epoxy resin is preferable. Further, the above component (D) may be used singly or in combination of two or more.

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

(E) component: inorganic black pigment

The component (E) which can be used in the present invention may, for example, be titanium black, carbon black or cobalt black, and is preferably titanium black from the viewpoint of good transmittance of light having a wavelength of 360 nm and 405 nm.

The content of the component (E) in the photosensitive resin composition is preferably 0.1 part by mass or more, and preferably 0.2 or less, based on 100 parts by mass of the total of the components (A) and (B). More than the mass. The viewpoint of excellent adhesion and resolution is preferably 10 parts by mass or less, preferably 5 or less. The amount is below.

The photosensitive resin composition containing the above components may further contain a dye such as malachite green, a photochromic agent such as tribromophenylphosphonium or reduced crystal violet, a thermochromic inhibitor, or p-toluene. Plasticizers such as guanamine, pigments other than black, fillers, defoamers, flame retardants, stabilizers, adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, perfumes, imaging agents, heat The crosslinking agent or the like is 0.01 to 20 parts by mass per 100 parts by mass of the total of the components (A) and (B). These may be used singly or in combination of two or more.

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

The method of forming the photosensitive resin composition layer on the substrate for an image display device using the obtained photosensitive resin composition is not particularly limited, and a photosensitive resin composition can be applied as a liquid photoresist to the substrate. And dry method. Further, a protective film may be coated on the photosensitive resin composition layer as needed. Further, it is preferred to use a photosensitive resin composition layer in the form of a photosensitive element, which will be described in detail later. The protective film used when the protective film is applied as a liquid photoresist is used, and examples thereof include a polymer film such as polyethylene or polypropylene.

The photosensitive resin composition is such that the photosensitive resin composition is photocured The 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 at an elongation of 25 ° C was 40% or more. The elongation is 40% or more, preferably 60% or more, from the viewpoint of suppressing breakage at the time of bending. The elongation of the cured product can be adjusted by reducing the crosslinking density of the cured product by a combination of the components (A) and (B).

Here, the photocuring of the photosensitive resin composition is carried out by forming a partition wall using the photosensitive resin composition, exposing it with necessary energy, and performing development as needed. The energy is preferably such that the number of remaining stages after development of the 41-stage stage exposure meter is 29.0.

A specific measurement method of the elongation of the cured product can be used: the cured product is formed into a sheet shape having a width of 10 mm and a thickness of 45 μm, and is stretched to a fixed speed at a temperature of 25 ° C, a distance between the chucks of 50 mm, and a speed of 2 cm/min. The method in which the cured product is broken and the elongation (%) is obtained by the following formula.

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

Moreover, it is preferable that the photosensitive resin composition is not broken in the following cases: a photosensitive resin composition layer composed of the photosensitive resin composition is formed on the transparent electrode, and the photosensitive resin composition is formed. After the layer photohardening, the mixture was heated at 120 ° C for 1 hour under air, and a DC voltage of 80 V was applied to the transparent electrode at 60 ° C and 90% RH for 100 hours.

Here, the photocuring of the photosensitive resin composition layer is carried out by forming the partition wall using the photosensitive resin composition layer, exposing it with necessary energy, and performing development as needed. The above energy is preferably such that the 41 stage The number of remaining stages after development of the exposure meter was 29.0.

The specific determination method for the dissolution of the transparent electrode is to test the impedance value of the anode by the tester, and determine that the measurable person is not broken due to dissolution, and the unmeasured person judges that the disconnection is caused by dissolution. Further, for the measurable person, the rate of increase from the initial impedance value can also be obtained.

(photosensitive element)

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention. As shown in Fig. 1, the photosensitive element 10 of the present invention comprises a support 1; a photosensitive resin composition layer 2 formed on the support 1, and a photosensitive resin composition layer 2 made of the photosensitive resin composition. And a protective film 3 formed on the photosensitive resin composition layer 2. Further, the protective film 3 may be provided as needed.

As the support 1, 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 from about 1 to 100 μm, preferably from 5 to 50 μm, more preferably from 10 to 30 μm. Further, when the support 1 is transparent, it is preferable to expose the photosensitive resin composition layer 2 by passing through the support 1 and exposing it.

The method of forming the photosensitive resin composition layer 2 on the support 1 is not particularly limited, but it is preferably carried out by applying a solution of the photosensitive resin composition and drying it. The thickness of the applied photosensitive resin composition layer varies depending on the desired characteristics, but the thickness after drying is preferably about 10 to 100 μm, preferably 20 to 100 μm, more preferably 30 to 100 μm, and particularly preferably 40~100μm.

The coating can be carried out, for example, by a conventional method such as a roll coater, a notch coater, a gravure coater, an air knife coater, a die coater, a bar coater, or the like. Drying can be carried out, for example, at 70 to 150 ° C for about 2 to 30 minutes. In addition, the amount of the organic solvent remaining in the photosensitive resin composition layer 2 is preferably 2% by mass or less from the viewpoint of preventing the organic solvent from diffusing in the subsequent step.

The protective film 3 may be laminated on the photosensitive resin composition layer 2 formed on the support 1 to coat the surface of the photosensitive resin composition layer 2. In the protective film 3, it is preferable that the adhesion between the photosensitive resin composition layer 2 and the protective film 3 is smaller than the adhesion between the photosensitive resin composition layer 2 and the support 1, and polyethylene can be used. An olefin-based film such as polypropylene or a polyester film typified by polyethylene terephthalate. When a polyester film is used as the support 1 and a polyester film of the same type is used as the protective film 3, it is preferred to use a surface treated with the surface of the protective film 3 in contact with the photosensitive resin composition layer.

Moreover, the protective films 3 are preferably films of low fish eyes. Here, "fisheye" means that when a film is produced by heating, melting, kneading, extrusion molding, biaxial stretching, casting, etc., foreign matter, undissolved matter, oxidative degradation, etc. of the material are ingested. In the film. That is, the "low fisheye" means that the foreign matter or the like in the film is small.

Further, the photosensitive element 10 may have an intermediate layer of a buffer layer, an adhesive layer, a light absorbing layer, a gas barrier layer or the like in addition to the photosensitive resin composition layer 2, the support 1, and any protective film 3. The protective layer.

The photosensitive element 10 to be produced is generally wound around a cylindrical core and stored. Moreover, at this time, it is preferable to wind up the support body 1 as an outer side. In the end surface of the above-mentioned roll-shaped photosensitive element roller, it is preferable to provide an end face spacer from the viewpoint of end face protection, and it is preferable to provide a moisture-proof end face spacer from the viewpoint of edge-resistant fusion. Here, the edge fusion system means a phenomenon in which the photosensitive resin composition layer 2 oozes from the end surface, and this phenomenon is also called cold flow. If this happens, it will become a source of foreign matter when forming a partition wall, which is a poor phenomenon. Moreover, as a packing method, it is preferable to package and pack a black sheet which is small in moisture permeability and is excellent in light-shielding property. The material of the above-mentioned winding core may, for example, be a plastic such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin or an ABS resin (acrylonitrile-butadiene-styrene copolymer).

(Method of Forming Partition Wall of Image Display Device, Method of Manufacturing Image Display Device, and Image Display Device)

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

First, as shown in FIG. 2(a), the electrode substrate 30 composed of the electrode 4 and the substrate 5 is prepared, and as shown in FIG. 2(b), the photosensitive element 10 is laminated on the electrode substrate 30. Photosensitive resin composition layer 2 and support 1 (layering step).

The substrate 5 constituting the electrode substrate 30 is not particularly limited as long as it is a substrate having flexibility, and examples thereof include an insulating substrate of a polymer film substrate and a semiconductor substrate such as a ruthenium substrate. As the electrode substrate 30, for example, such as ITO, IZO, Ag wires are formed on the substrate 5. The electrode 4 of the ink having flexibility. As a method of forming the electrode 4, for example, A method of forming a pattern by a photolithographic etching method using an electrode material laminated by a method such as vapor deposition or sputtering, or a method of patterning a photosensitive electrode material. The method of forming the electrode 4 is not particularly limited.

As a method of laminating the photosensitive resin composition layer 2 on the electrode substrate 30, in addition to the above-described method of using the photosensitive element 10, a solution of the photosensitive resin composition may be applied onto the electrode substrate 30 and dried. method.

When the protective film 3 is present on the photosensitive resin composition layer 2, the method of laminating the photosensitive element 10 is laminated on the electrode substrate 30 while removing the protective film 3. For example, the photosensitive resin composition layer 2 is heated to about 70 to 130 ° C, and is pressure-bonded to the electrode substrate 30 at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf/cm ² ) to perform a layer. The combination method or the like can also be carried out under reduced pressure. The shape of the surface of the electrode substrate 30 is generally formed by an electrode pattern, but may be flat or irregular as necessary.

After the photosensitive resin composition layer 2 is laminated, as shown in FIG. 2(b), the photosensitive resin composition layer 2 is irradiated with the active light ray 8 in an image form, and the exposed portion is photocured (exposure step). As shown in FIG. 2(b), a mask pattern 7 is provided on the photosensitive resin composition layer 2, and the active light ray 8 is irradiated in an image form to expose the exposure portion. A method of photocuring the photosensitive resin composition layer 2. The mask pattern 7 can be either a negative type or a positive type, and can be used by a general user. As the light source of the active light 8, a conventional light source such as a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp or the like can be used to effectively emit ultraviolet rays or visible light. also, The exposure method can also be a direct delineation exposure method in which the pattern is directly drawn by laser without using the mask pattern 7.

After the exposure, as shown in FIG. 2(c), the photosensitive resin composition layer 2 of the unexposed portion is selectively removed by development, thereby being used on the substrate (electrode substrate 30) for the image display device. A photo hardening pattern 20 is formed (development step). Further, when the support 1 is present, the development step is to remove the support 1 before development.

The development can be carried out by removing the unexposed portion by wet development using a developing solution such as an aqueous alkaline solution, an aqueous developing solution or an organic solvent, or dry development. An alkaline aqueous solution is preferably used in the present invention. The alkaline aqueous solution may, for example, be a thin solution of 0.1 to 5% by mass of sodium carbonate, a thin solution of 0.1 to 5% by mass of potassium carbonate, or a thin solution of 0.1 to 5% by mass of potassium hydroxide. The pH of the alkaline aqueous solution is preferably adjusted to a range of from 9 to 11, and the temperature is adjusted in accordance with the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent or the like may be mixed in the alkaline aqueous solution. Examples of the development method include a dipping method, a spraying method, a brushing method, and a rinsing method. However, it is preferable to use a spray coating method for improving the resolution.

As the post-development treatment, it is preferred that the formed photo-cured pattern 20 is further cured by heat treatment at about 60 to 250 ° C as needed. The curing temperature is preferably about 80 to 200 ° C, preferably about 100 to 150 ° C. Further, the hardening time is not particularly limited, but it is preferably from 10 minutes to 3 hours, preferably from 30 minutes to 2 hours.

Further, the step of filling the display medium such as particles in the photo-cured material pattern 20 formed in the above step, and the photo-curing pattern 20 The step of adhering the other electrode substrate 30 ((d) and (e) of FIG. 2) and the like can complete the formation of the partition wall of the image display device and the manufacture of the image display device.

The step of adhering the photocured material pattern 20 to the other electrode substrate 30 can be carried out as follows. That is, the above steps are performed by laminating the adhesive 40 on the photo-cured pattern 20 as shown in FIG. 2(d), and then, as shown in FIG. 2(e), the adhesive 40 is followed by the electrode substrate 30. It is carried out with a photo-curing pattern 20 . Further, a transparent electrode substrate can be used at least on the electrode substrate on the display surface side of the image display device.

The image display device formed through the above-described respective steps includes the electrode substrate 30 having flexibility and the partition wall composed of the highly-curable light-cured material pattern 20, and excellent bending property can be achieved. In particular, by selecting the material of the electrode 4, an image display device having a high flexibility which can correspond to a curvature radius of about 5 to 15 mm can be obtained. Moreover, even when the image display apparatus is bent at a curvature radius of about 5 to 15 mm by using the partition wall formed of the photosensitive resin composition of the present invention, the occurrence of breakage can be sufficiently suppressed.

Example

Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the embodiments as long as the technical idea of the present invention is not exceeded.

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

After the components (A), (B), (C), (E), and other components shown in Table 1 were prepared, the component (D) shown in Table 1 was added and dissolved to obtain a solution. The photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 5. The amount of each component (unit: g) is shown in Table 1.

The details of the ingredients in Table 1 are as follows. Further, in the component (A), the following amounts were prepared by using a resin solution, but in Table 1, the amount of the solid component was shown.

(A) Ingredients: Adhesive polymer

*1: 48% by mass of 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 content 45g)

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

(B) component: photopolymerizable compound

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

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

*5: FA-023M (made by Hitachi Chemical Co., Ltd., trade name)

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

*7: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-decanoate (manufactured by Hitachi Chemical Co., Ltd., trade 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 hydrazine (manufactured by Sumitomo Seika Co., Ltd., product name: TPS)

*10: 1,7-bis(9-acridinyl)heptane (manufactured by ADEKA Co., Ltd., trade name: N-1717)

*11: Benzyl dimethyl ketal (manufactured by Ciba Specialty Chemical Co., Ltd., trade name: I-651)

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

*12: Cresol novolak 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 novolak 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 BL 3175)

*17: Block isocyanate (Sumitomo Bayer Urethane shares limited Company system, trade name: DESMODUR BL 3475)

*18: Block isocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name: DESMODUR VPLS 2253)

(E) component: inorganic black pigment

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

Other ingredients

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

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

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

The ITO surface of the PET substrate (manufactured by Toyobo Co., Ltd., trade name: R-300) with ITO is attached to the photosensitive resin composition layer. In the form of the surface of the PET substrate of ITO, the photosensitive element was laminated by heating to a laminating roll of 110 ° C while peeling off the polyethylene protective film. The structure of the obtained laminate is a PET substrate with ITO, a photosensitive resin composition layer, and a polyethylene terephthalate film from the bottom. For the obtained laminate, evaluation of sensitivity, adhesion, resolution, and sheet metal bending was performed.

<Evaluation of Sensitivity>

Using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) with a high-pressure mercury lamp, a photomask (PhotoTool) having a 41-stage stage exposure meter was adhered to the laminate of polyethylene terephthalate. The ester film was exposed and exposed. After the exposure, the polyethylene terephthalate film was peeled off and sprayed at 30 ° C for 20 seconds using a 1% by mass aqueous sodium carbonate solution, whereby the unexposed portion of the photosensitive resin composition layer was removed. The number of remaining phases after development of the 41-stage staged exposure meter was set to 29.0 energy (exposure amount) as sensitivity (mJ/cm ² ). The smaller the value of this energy, the higher the sensitivity. The evaluation results are shown in Table 2. Further, when exposure was performed with the above energy, the actual number of remaining stages is shown in Table 2.

<Evaluation of Adhesion>

A parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp is used, and the line width/pitch width as a negative film for adhesion evaluation is 10/300 to 80/300 (unit: μm, pitch) Wide-fixed wiring pattern photomask, and light mask with 41-stage stage exposure meter The laminate was adhered to a polyethylene terephthalate film of a laminate, and exposed to an energy of 29.0 after the development of the 41-stage staged exposure meter. After the exposure, the polyethylene terephthalate film was peeled off and sprayed at 30 ° C for 20 seconds using a 1% by mass aqueous sodium carbonate solution, thereby removing the unexposed portion of the photosensitive resin composition layer to evaluate the adhesion. . The adhesion is expressed by the minimum line width (μm) remaining without being peeled off by the developing solution. The smaller the value, the smaller the line can be, and the film is not peeled off from the glass substrate. The higher the sex. The evaluation results are shown in Table 2.

<Evaluation of Resolution>

A photomask having a 41-stage staged exposure meter and a photomask having a line width/pitch width of 30/30 to 200/200 (unit: μm) as a negative film for evaluation evaluation On the polyethylene terephthalate film of the laminate, a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high pressure mercury lamp was used to develop the 41-stage staged exposure meter. The number of remaining stages is 29.0 of energy for exposure. After the exposure, the polyethylene terephthalate film was peeled off and sprayed at 30 ° C for 20 seconds using a 1% by mass aqueous sodium carbonate solution, whereby the unexposed portion of the photosensitive resin composition layer was removed to evaluate the resolution. The resolution is expressed by the minimum pitch width (μm) at which the unexposed portion can be favorably removed by the development process, and the smaller the value, the better the resolution.

The evaluation results are shown in Table 2.

<Evaluation of Sheet Metal Bending>

A parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp was used to expose the energy having a residual phase of the stage after the development of the 41-stage staged exposure meter to 29.0. After the exposure, the polyethylene terephthalate film was peeled off and sprayed at 30 ° C for 20 seconds using a 1% by mass aqueous sodium carbonate solution, whereby the unexposed portion of the photosensitive resin composition layer was removed. Then, it was allowed to stand in a box type dryer (manufactured by Mitsubishi Electric Corporation, model: NV50-CA, air atmosphere) heated to 120 ° C for 1 hour. The obtained evaluation piece was subjected to sheet metal bending, and the cured product of the photosensitive resin composition layer was not peeled off from the PET substrate to which ITO was attached, and the damage was found to be A, and the PET base to which ITO was attached was found. If the material is stripped, or if it is found to be damaged, it is rated as B.

<Solubility of Electrode>

On the IZO-TEG (Test Element Group) substrate, the IZO and ITO surfaces of the ITO-TEG (Test Element Group) substrate, the photosensitive resin composition layer is in contact with the surface of the IZO-TEG substrate and the ITO-TEG substrate, respectively. The photosensitive element was laminated by heating to a laminating roll of 110 ° C while peeling off the protective film made of polyethylene. The structure of the obtained laminate is a TEG substrate, a photosensitive resin composition layer, and a polyethylene terephthalate film from the bottom. A photomask having a 41-stage stage exposure meter was adhered to the laminate polyethylene terephthalate film, and a parallel light exposure machine EXM-1201 having a high pressure mercury lamp was used (Oak Co., Ltd. The exposure was performed with an energy of 29.0 after the development. After exposure, the polyethylene terephthalate film is peeled off, and The unexposed portion of the photosensitive resin composition layer was removed by spraying with a 1% by mass aqueous sodium carbonate solution at 30 ° C for 20 seconds. Thereby, an evaluation substrate in which the photocured material of the photosensitive resin composition layer was formed on the TEG substrate was obtained. Then, the obtained evaluation substrate was placed in a box type dryer (manufactured by Mitsubishi Electric Corporation, model: NV50-CA) heated to 120 ° C for 1 hour. Then, a DC voltage of 80 V was applied to the electrodes of the evaluation substrate under conditions of 60 ° C and 90% RH, and the anode resistance value after 100 hours was measured by a tester. The evaluation results are shown in Table 2. In the table, A indicates that the impedance value can be measured, and it is judged that the disconnection is not caused by the dissolution, and B indicates that the measurement cannot be performed, and it is determined that the disconnection is caused by the dissolution. Further, for A, the anode resistance value after 100 hours was divided by the initial impedance value and multiplied by 100 times to record the impedance increase rate (%). The smaller the value of the impedance rise rate, the more it is possible to suppress the dissolution of the electrode.

<Extension of hardened material>

The photosensitive member is peeled off from the surface of the polytetrafluoroethylene sheet so that the photosensitive resin composition layer contacts the surface of the polytetrafluoroethylene sheet on the polytetrafluoroethylene sheet (manufactured by Nitto Denko Corporation, product name: Nittoflon Film No. 900U). The vinyl protective film was laminated while being heated to a laminating roll of 110 °C. The structure of the obtained laminate was a sequence of a polytetrafluoroethylene sheet, a photosensitive resin composition layer, and a polyethylene terephthalate film. Exposure was carried out from a polyethylene terephthalate film of the above laminate using a parallel light exposure machine EXM-1201 (manufactured by Oak Co., Ltd.). Moreover, the exposure of the laminate is such that after the development of the 41-stage staged exposure meter The number of storage stages is increased by 29.0. After the exposure, the polyethylene terephthalate film was peeled off and sprayed at 30 ° C for 30 seconds using a 1% by mass aqueous sodium carbonate solution to remove the unexposed portion of the photosensitive resin composition layer. Thereby, an evaluation piece in which the photocured material of the photosensitive resin composition layer was formed on the polytetrafluoroethylene sheet was obtained. Then, the obtained evaluation piece was allowed to stand in a box type dryer (manufactured by Mitsubishi Electric Corporation, model: NV50-CA, air atmosphere) heated to 120 ° C for 1 hour. The heat-treated evaluation piece was cut into a width of 10 mm, and the distance between the chucks was 50 mm, and the cured product of the photosensitive resin composition layer was broken at a fixed speed of 2 cm/min. Elongation (%) of the cured product at 25 °C. The evaluation results are shown in Table 2.

From the results shown in Table 2, it was confirmed that the presence of the component (D) suppressed the dissolution of the electrode. Further, regarding the elongation, it was confirmed that 40% or more of the high elongation property was obtained, and the breakage of the partition wall at the time of bending was suppressed.

Industrial availability

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

1‧‧‧Support

2‧‧‧Photosensitive resin composition layer

3‧‧‧Protective film

4‧‧‧Electrode

5‧‧‧Substrate

10‧‧‧Photosensitive components

20‧‧‧The cured product of the photosensitive resin composition (light cured product pattern)

30‧‧‧Electrode substrate

40‧‧‧Binder

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention.

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

1‧‧‧Support

2‧‧‧Photosensitive resin composition layer

3‧‧‧Protective film

10‧‧‧Photosensitive components

Claims (15)

A photosensitive resin composition which is a photosensitive resin composition for forming a partition wall separating pixels, the image display device having a curved shape having a transparent electrode at least on a display surface In the image display device, the photosensitive resin composition contains the component (A): a binder polymer having a carboxyl group in the molecule, (B) a component: a photopolymerizable compound, (C) component: a photopolymerization initiator, and (D) Component: a compound having an epoxy group in the molecule; and (E) component: an inorganic black pigment, wherein the photosensitive resin composition is photocured and then heated at 120 ° C for 1 hour in air to have a width of 10 mm and a thickness of 45 μm. The sheet-like cured product has an elongation at 25 ° C of 40% or more. The photosensitive resin composition of claim 1, wherein the component (E) contains titanium black. The photosensitive resin composition of claim 1 or 2, wherein the component (A) is an acrylic resin. The photosensitive resin composition of claim 1 or 2, wherein the component (A) is an acrylic copolymer containing methacrylic acid, methyl methacrylate, and butyl methacrylate. The photosensitive resin composition according to claim 1 or 2, wherein the component (B) contains the component (B1): a compound having a trimeric isocyanate ring structure. a photosensitive resin composition as claimed in claim 1 or 2, The component (B) contains the component (B2): polyolefin glycol di(meth)acrylate. The photosensitive resin composition of claim 1 or 2, wherein the component (C) contains a benzyl derivative. The photosensitive resin composition of claim 1 or 2, wherein the component (C) contains an acridine derivative. The photosensitive resin composition according to claim 1 or 2, wherein the component (D) contains a dicyclopentadiene type epoxy resin and/or a cresol novolak type epoxy resin. A photosensitive element comprising: a support and a photosensitive resin composition layer formed on the support, the photosensitive resin composition layer being photosensitive according to any one of claims 1 to 9 It is composed of a resin composition. A method for forming a partition wall of an image display device, comprising: a partition wall disposed at least on a transparent electrode of a display surface and a separation pixel, and having flexibility, the method having the following steps: in the image display device a laminating step of laminating a photosensitive resin composition layer composed of a photosensitive resin composition according to any one of claims 1 to 9; and irradiating active light to the photosensitive resin composition layer The specific portion is an exposure step of photocuring the exposed portion; and a portion other than the exposed portion of the photosensitive resin composition layer is removed to form a development step of the photocured pattern. Method for manufacturing image display device, the image display device A partition having at least a partition wall of a transparent electrode and a separate pixel disposed on a display surface and having flexibility, the method having the step of forming the partition wall by the method of claim 11 of the patent application. The method of producing an image display device according to claim 12, wherein the transparent electrode is made of a material formed by applying a solution containing at least one type of metal conductive fiber. The method of manufacturing an image display device according to claim 12, further comprising the step of filling the display medium in the partition wall; and adhering the substrate to the partition wall by facing the substrate on the other side Side steps. An image display device manufactured by the method of manufacturing an image display device according to any one of claims 12 to 14.