JP4935833B2 - Photosensitive resin composition, photosensitive element using the same, method for forming partition of image display device, and method for manufacturing image display device - Google Patents

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, and a method for manufacturing 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 an alternative to paper in terms of environment and cost. Practical application is being attempted.

  As a display technique of an image display device, various types such as a type in which particles are moved by electrophoresis, a liquid crystal type, an electrochemical type, and the like 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 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 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 is a report example of realizing full color display by combining a color filter with white / black image display (see, for example, Non-Patent Document 2).

  When performing such 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.

  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, and further forming a photosensitive resin composition layer by applying a photosensitive resin composition or laminating a photosensitive film on the light-shielding layer 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. 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.

  In the case of manufacturing an image display device, the method further includes a step of filling a display medium such as particles in the pattern obtained in the step, a step of heat-treating the photocured product pattern, a step of attaching an electrode substrate, and the like. An image display device using the cured product of the composition layer as a partition is obtained. Since a high temperature process is indispensable in the process, heat resistance and the like are required for the partition walls of the image display device formed using the photosensitive resin composition.

  In recent years, attempts have been made to realize flexibility in such image display devices (see, for example, Non-Patent Document 3). Along with this, the substrate of the image display device has moved from a rigid substrate such as a glass substrate on which electrodes are formed of ITO or the like to a flexible substrate such as a PET (polyethylene terephthalate) substrate or an FPC substrate. ing.

  When realizing such flexibility, it is essential to deal with the flexibility of the partition walls separating the pixels. Therefore, a partition with a low elastic modulus is required.

  On the other hand, when the elasticity of the photosensitive element is reduced, the resolution and adhesion tend to decrease. In order to increase the display area, it is necessary to improve the resolution of the partition walls in order to improve the contrast between the pixels of the image display device. It is also necessary to shield the light between the pixels.

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) Naoki Tanaka, “Electronic Paper Start”, MICRODEVICES, April 1, 2008, MICRODEVICES 274: 31-45 (2008)

  In the conventional method for forming a partition wall of an image display device using a photosensitive resin composition, it is necessary to laminate a light shielding layer and a partition wall as described above, which increases the number of processes and increases the cost of materials. there were.

  Moreover, when a black pigment was added to the conventional photosensitive resin composition to form a light-shielding partition, sensitivity, resolution, and adhesion to the substrate were insufficient. In addition, there is a problem that the pattern cannot be peeled off or cracked due to failure to follow the flexible substrate.

  Furthermore, even when a partition is formed using a photosensitive resin composition that can be used for a cover lay of a flexible printed wiring board (FPC) or the like to obtain a cured product having relatively low elasticity, an image display device such as paper can be used. It has not yet been realized, and the adhesion to the substrate was insufficient.

  The present invention has been made in view of the above problems, and it is easy to form a partition wall for an image display device having excellent light shielding properties, low elastic modulus of a cured film, high adhesion, and high resolution with good workability. The photosensitive resin composition which can be manufactured, the photosensitive element using the same, the formation method of the partition of an image display apparatus, and the manufacturing method of an image display apparatus are provided.

The present invention provides [1] a photosensitive resin composition for forming a partition wall of an image display device, wherein the photosensitive resin composition comprises:
(A) a binder polymer having a carboxyl group,
(B) a photopolymerizable compound,
(C) a photopolymerization initiator and (D) an inorganic black pigment, wherein the (B) photopolymerizable compound is (B1) a compound having an ethylenically unsaturated group and a urethane bond in the molecule; and (B2 And a compound having an ethylenically unsaturated group and an oxyethylene group and / or oxypropylene group in the molecule, and the total number n of the oxyethylene group and / or oxypropylene group is 16 to 100. A photosensitive resin composition is provided.

  Since the photosensitive resin composition of the present invention has the above-described configuration, the cured film after heat curing has a low elastic modulus, excellent light shielding properties, high adhesion, and a partition for an image display device with high resolution. It can be formed with good workability.

  The present invention also provides [2] the photosensitive resin composition according to the above [1], wherein the component (B1) includes a compound having an isocyanuric ring structure. Thereby, a low elasticity cured film can be obtained and the adhesiveness to a flexible substrate can be improved.

  The present invention also provides [3] the photosensitive resin composition according to the above [1] or [2], wherein the component (B1) comprises a compound having a weight average molecular weight of 2,000 to 10,000. Thereby, a further low elasticity cured film can be obtained, and the adhesiveness to a flexible substrate can be further improved.

  The present invention also provides: [4] The component (B2) is an oxyethylene group (EO) or oxypropylene group (PO) -modified bisphenol A-based (meth) acrylate compound, a polyalkylene glycol di (meth) acrylate compound, and The photosensitive resin composition according to any one of the above [1] to [3], comprising at least one selected from the group consisting of, (EO) or (PO) -modified trimethylolpropane tri (meth) acrylate compounds. To do. Thereby, resolution and adhesiveness can be improved, maintaining the low elasticity of a cured film.

  Moreover, this invention is [5] the photosensitive resin in any one of said [1]-[4] in which the said (B) component further contains the compound represented by (B3) following General formula (1). A composition is provided. Thereby, the resolution can be further improved.

［一般式（１）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 General Formula (1), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, a methyl group or a halogenated methyl group, R ⁵ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, Any one of a hydroxyl group is shown, p shows the integer of 0-4. 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. ]

  The present invention also provides [6] the photosensitive resin composition according to any one of the above [1] to [5], wherein the (D) inorganic black pigment contains titanium black. Thereby, light-shielding property is further excellent and thermal stability can be improved.

  [7] The present invention provides [7] in any one of [1] to [6] above, wherein a cured film thermally cured at 120 ° C. for 1 hour has a tensile elastic modulus at a film thickness of 45 μm of 1 GPa or less at 25 ° C. The photosensitive resin composition is provided. Thereby, the partition which can respond to a flexible substrate can be formed.

Further, the present invention provides [8] a support, and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of the above [1] to [7] formed on the support, A photosensitive element is provided.
The photosensitive element of the present invention comprises a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention, so that the cured film after heat curing has a low elastic modulus, excellent light shielding properties, high adhesion, A partition wall for a high-resolution image display device can be easily formed with good workability.

  Moreover, this invention provides the photosensitive element as described in said [8] whose film thickness of [9] the said photosensitive resin composition layer is 10-60 micrometers. Thereby, it is possible to form a partition wall for an image display device having excellent light shielding properties, high adhesion, and high resolution.

  The present invention also provides [10] a lamination step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to [7] above on a substrate of an image display device; An exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photocure the exposed portion, and a developing step of removing a portion other than the exposed portion to form a photocured product pattern. A method for forming a partition wall of an image display device is provided.

  The present invention further includes [11] a heating step of heat-curing the photocured product pattern formed by the method for forming a partition wall of the image display device according to [10] at 60 to 250 ° C. A method for forming a partition wall of an image display device is provided.

The present invention also provides [12] The method for forming a partition wall of the image display device according to [10] or [11], wherein the substrate is a flexible substrate.
Further, according to the present invention, the display medium such as particles is filled in the partition formed by the method for forming a partition of the image display device according to any one of [10] to [12]. There is provided a method for manufacturing an image display device, which includes a step and a step of attaching a substrate to the opposite side of a partition so as to face one substrate.

  According to the present invention, there is provided a photosensitive resin composition that is excellent in light-shielding properties, has a low cured film elastic modulus, and can easily form a partition for an image display device having high adhesion and high resolution with good workability. It is possible to provide a photosensitive element using the above, a method of forming a partition wall of an image display device, and a method of manufacturing an image display device.

  Hereinafter, preferred embodiments of the present invention will be described. In this 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.

  Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.

  The photosensitive resin composition of the present invention comprises (A) a binder polymer having a carboxyl group, (B) a photopolymerizable compound [(B1) compound and (B2) compound], (C) a photopolymerization initiator, and (D). Contains inorganic black pigment. Hereinafter, each component will be described in detail.

  (A) The binder polymer having a carboxyl group contains a carboxyl group from the viewpoint of alkali developability, and is produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. can do. The polymerizable monomer having a carboxyl group is preferably (meth) acrylic acid from the viewpoints of developability and stability.

  Moreover, it is preferable that (A) binder polymer contains styrene or a styrene derivative as a copolymerization component from an adhesive viewpoint. (A) Content in case a binder polymer contains styrene or a styrene derivative is 5-45 mass% with respect to all the copolymerization components from a viewpoint of improving adhesiveness and the low elasticity of a cured film with sufficient balance. It is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass.

  (A) The acid value of the binder polymer having a carboxyl group is preferably 30 mgKOH / g or more from the viewpoint of resolution, and preferably 250 mgKOH / g or less from the viewpoint of developer resistance and adhesion, More preferably, it is 80-240 mgKOH / g, More preferably, it is 130-230 mgKOH / g, It is especially preferable that it is 180-220 mgKOH / g. When performing development with a solvent as the development step, it is preferable to prepare while suppressing the amount of polymerizable monomer having a carboxyl group.

  (A) The weight average molecular weight of the binder polymer having a carboxyl group (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) is 20,000 or more from the viewpoint of developer resistance. In view of shortening the development time, it is preferably 300,000 or less, more preferably 25,000 to 150,000, and particularly preferably 30,000 to 70,000.

  In the present invention, (A) the binder polymer having a carboxyl group may be used in combination with other binder polymers, such as acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyds. Resin, phenol resin and the like. An acrylic resin is preferable from the viewpoint of alkali developability. These can be used alone or in combination of two or more binder polymers. 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, and two or more types of binder polymers having different degrees of dispersion. 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 binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, and p-ethyl styrene, and vinyl alcohols such as acrylamide, acrylonitrile, and vinyl n-butyl ether. Esters of (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) Maleic acid monoesters such as crylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic Examples include acids, itaconic acid, crotonic acid, propiolic acid and the like. These may be used alone to form a homopolymer, or two or more types may be combined to form 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. These can be used alone or in combination of two or more.

  The photopolymerizable compound of the component (B) in the present invention contains the compound (B1) and the compound (B2). The (B1) compound is a compound having an ethylenically unsaturated group and a urethane bond in the molecule, and the (B2) compound has an ethylenically unsaturated group and an oxyethylene group and / or oxypropylene group in the molecule. And the total number of repeating oxyethylene groups and / or oxypropylene groups is 11-100.

  The compound (B1) preferably further contains a compound (b1) having an isocyanuric ring structure. Examples of the compound (b1) having an isocyanuric ring structure include compounds represented by the following general formula (2).

一般式（２）中、Ｒ^１は、各々独立に、

In general formula (2), each R ¹ is independently

（一般式（３）中、Ｒ^２は、水素原子又はメチル基を示し、ｍは１〜１４の整数である）、

(In General Formula (3), R ² represents a hydrogen atom or a methyl group, and m is an integer of 1 to 14),

（一般式（４）中、ｍは１〜１４の整数である）、又は、

(In General Formula (4), m is an integer of 1 to 14), or

（一般式（５）中、Ｒ^２は水素原子又はメチル基を示し、ｎは１〜９の整数であり、ｍは１〜１４の整数である）を示し、Ｒ^１のうち少なくとも１つは一般式（５）である。
弾性率、密着性の観点から一般式（２）中のＲ^１のうち２つは、一般式（５）であることがより好ましく、Ｒ^１の全てが一般式（５）であることがさらに好ましい。

(In General Formula (5), R ² represents a hydrogen atom or a methyl group, n is an integer of 1 to 9, and m is an integer of 1 to 14), and at least one of R ¹ is It is General formula (5).
From the viewpoint of elastic modulus and adhesiveness, two of R ^{1 in} the general formula (2) are more preferably the general formula (5), and all of R ¹ are further the general formula (5). preferable.

  In general formulas (3) and (4), m is an integer of 1 to 14, and preferably 1 to 6. When m exceeds 14, chemical resistance may deteriorate. Moreover, in General formula (5), m is an integer of 1-14, it is preferable that it is 1-6, n is an integer of 1-9, and it is preferable that it is 3-6. When m exceeds 14, chemical resistance may be reduced, and when n exceeds 9, mechanical strength may be reduced.

A compound represented by the above following general formula (2), those commercially available, for example, NK Oligo UA-21eb (Shin-Nakamura Chemical Co., Ltd., trade name, in the general formula (2), R1 is any formula (5)).

  In addition, the compound (B1) is a urethane compound having a urethane bond derived from the reaction between the hydroxyl group at the terminal of the polycarbonate compound and / or the polyester compound and the isocyanate group of the diisocyanate compound, and having an isocyanate group at a plurality of terminals. And a compound (b2) that can be obtained by a condensation reaction between a hydroxyl group and a compound having an ethylenically unsaturated group.

  (B2) The urethane compound used for the synthesis of the compound is a polycarbonate compound and / or a polyester compound having hydroxyl groups at both ends (hereinafter referred to as “(1) polycarbonate compound” and “( 2) Polyester compound ”) and a diisocyanate compound (hereinafter sometimes referred to as“ (3) diisocyanate compound ”) can be obtained. In particular, from the viewpoint of obtaining a cured film having low elasticity, it is preferable to use a urethane compound obtained by reacting (2) a polyester compound and (3) a diisocyanate.

  (1) A polycarbonate compound has a structure in which an alkylene group is arranged in a main chain through a carbonate bond, and can be obtained by a known method. For example, when a polycarbonate compound is obtained by a phosgene method, a diol compound and phosgene are obtained. And react. Examples of the diol compound include diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polypropylene glycol, erylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2 -Methyl-1,3-butanediol, neopentyl glycol, 2-methylpentanediol, 3-methylpentanediol, 2,2,4-trimethyl-1,6-hexanediol, 3,3,5-trimethyl-1 , 6-hexanediol, 2,3,5-trimethyl-pentanediol, 1,6-hexanediol, 1,5-pentanediol, etc., which are used alone or in combination of two or more. Is done. Further, polyol compounds such as trimethylolpropane, trimethylolethane, hexanetriol, heptanetriol, pentaerythritol may be contained.

  Among the polycarbonate compounds, hexamethylene carbonate represented by the following general formula (I) derived from 1,6-hexanediol and 1,5-pentanediol and pentamethylene carbonate represented by the following general formula (II) The thing containing is preferable.

  The molar ratio of hexamethylene carbonate and pentamethylene carbonate contained in the polycarbonate compound is preferably hexamethylene carbonate / pentamethylene carbonate = 1/9 to 9/1. When this content ratio is out of the above range, the elongation and strength of the photocured product tend to decrease.

  (2) The polyester compound can be obtained by a known method by polycondensation of a polybasic acid and a polyhydric alcohol. Examples of the polybasic acid include aromatic and aliphatic dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, and sebacic acid. Examples of the polyhydric alcohol include glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, hexanediol, neopentyl glycol, diethylene glycol, and triethylene glycol.

  The polycarbonate compound and the polyester compound preferably have a weight average molecular weight (for example, measured by GPC and converted to polystyrene) of 600 to 1,000. If the weight average molecular weight is outside the above range, the elongation and strength of the photocured product tend to decrease.

  (3) Examples of the diisocyanate compound include an aliphatic diisocyanate compound having a divalent aliphatic group such as an alkylene group, an alicyclic diisocyanate compound having a divalent alicyclic group such as cycloalkylene, and an aromatic diisocyanate. Examples of the compound include these isocyanurate-modified products, carbodiimidization-modified products, and biuret-modified products.

  Examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. Examples of the alicyclic diisocyanate compound include isophorone diisocyanate, methylene bis (cyclohexyl) diisocyanate, and 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane. As aromatic diisocyanate compounds, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-triene diisocyanate or dimerized polymer of 2,6-triene diisocyanate, (o, p or m) -xylene diisocyanate , Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate. These are used individually by 1 type or in combination of 2 or more types. Moreover, the isocyanate compound which has 2 or more isocyanate groups, such as a triphenylmethane triisocyanate and a tris (isocyanate phenyl) thiophosphate, may be contained. Among these, an alicyclic diisocyanate compound is preferable and isophorone diisocyanate is more preferable from the viewpoint of achieving a higher level of flexibility and toughness of the photocured product.

  A urethane compound having an isocyanate group at a plurality of terminals (hereinafter, referred to as “(4) urethane compound” in some cases) includes (1) a polycarbonate compound and / or (2) a polyester compound and (3) a diisocyanate compound. It is obtained by reacting. (4) The urethane compound preferably has an isocyanate group at both ends. In this case, in the above reaction, (3) the diisocyanate compound is used in a total amount of 1 mol of the polycarbonate compound and (2) the polyester compound. The blending amount is preferably 1.01 to 2.0 mol, and more preferably 1.1 to 2.0. (3) When the amount of the diisocyanate compound is less than 1.01 mol or exceeds 2.0 mol, there is a tendency that a urethane compound having an isocyanate group at both ends cannot be obtained stably. In the reaction for synthesizing the urethane compound (4), it is preferable to add a catalyst such as dibutyltin dilaurate. From the viewpoint of sufficiently advancing the reaction, the reaction temperature is preferably 60 to 120 ° C.

  A compound having a hydroxyl group and an ethylenically unsaturated group in the molecule (hereinafter referred to as “(5) hydroxyl group-containing ethylenically unsaturated group), which can be used in the reaction for reacting with the urethane compound to obtain the compound (b2). Examples of the “compound”) include compounds having a hydroxyl group and a (meth) acryloyl group in the molecule. Examples of such compounds include hydroxy (meth) acrylates, caprolactone adducts or alkylene oxide adducts thereof, ester compounds of polyhydric alcohols such as glycerin and (meth) acrylic acid, and glycidyl (meth) arylate acrylic acid. Addenda may be mentioned.

  As hydroxy (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate are mentioned, for example. Examples of these caprolactone adducts include hydroxyethyl (meth) acrylate / caprolactone adduct, hydroxypropyl (meth) acrylate / caprolactone adduct, hydroxybutyl (meth) acrylate / caprolactone adduct, and alkylene oxide adduct. Examples thereof include hydroxyethyl (meth) acrylate / alkylene oxide adduct, hydroxypropyl (meth) acrylate / propylene oxide adduct, and hydroxyethyl (meth) acrylate / butylene oxide adduct. Examples of ester compounds include glycerin mono (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane mono (meth) acrylate, and ditrimethylolpropane. Examples thereof include tri (meth) acrylate, di (meth) acrylate of ethylene oxide adduct of trimethylolpropane, and di (meth) acrylate of propylene oxide adduct of trimethylolpropane. These are used individually by 1 type or in combination of 2 or more types.

  The (b2) compound is obtained by subjecting (4) a urethane compound to an addition reaction of (5) a hydroxyl group-containing ethylenically unsaturated compound. In such an addition reaction, it is preferable that the amount of (5) the hydroxyl group-containing ethylenically unsaturated compound is 2.0 to 2.4 moles per mole of (4) urethane compound. (5) If the amount of the hydroxyl group-containing ethylenically unsaturated compound is less than 2.0 mol, the photopolymerization tends to be insufficient, and if it exceeds 2.4 mol, the elongation of the photocured product and There is a tendency for strength to decrease. The above addition reaction is preferably carried out in the presence of, for example, p-methoxyphenol, di-t-butyl-hydroxy-toluene, etc. In addition, it is preferable to add a catalyst such as dibutyltin dilaurate. The reaction temperature is preferably 60 to 90 ° C. When the temperature is lower than 60 ° C., the reaction tends not to proceed sufficiently, and when the temperature exceeds 90 ° C., gelation tends to occur due to rapid heat generation. The end point of the reaction may be, for example, the time when the isocyanate group disappears in the infrared absorption spectrum.

  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, a hydroxyl group and an ethylenically unsaturated group The weight average molecular weight of the compound that can be obtained by the condensation reaction of the compound having an amount of 200 to 100,000 is from the viewpoint of improving the compatibility with the component (A) and the low elasticity of the cured film in good balance. It is preferably 1000 to 50000, more preferably 2000 to 20000, and particularly preferably 2,000 to 10,000.

  (B1) A compound may be synthesize | combined by a conventional method and a commercially available thing may be obtained. Available (B1) compounds include, for example, UF-8003M, UF-TCB-50, UF-TC4-55 (above trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and hyaloid 9082-95 (trade name, Hitachi Chemical Co., Ltd.). Manufactured by the same company).

  Furthermore, as the (B1) compound other than those described above as the component (B), 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 Examples include addition reaction products with diisocyanate compounds such as 1,6-hexamethylene diisocyanate, EO-modified urethane di (meth) acrylate, and EO, PO-modified urethane di (meth) acrylate. Examples of the EO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., product name UA-11, and the like. Examples of EO and PO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., product name UA-13, and the like. These may be used alone or in combination of two or more.

  The component (B) has an ethylenically unsaturated group and an oxyethylene group and / or oxypropylene group in the molecule as the compound (B2), and the total number of repeating oxyethylene groups and / or oxypropylene groups is Including compounds that are 11-100. When the (B2) compound has both an oxyethylene group and an oxypropylene group, these copolymer chains may be block or random. The total number of repeating oxyethylene groups and / or oxypropylene groups is preferably 15 to 90, more preferably 15 to 50, from the viewpoint of improving the adhesion and low elasticity of the cured film in a balanced manner. More preferably, it is 15-30.

  (B2) Compounds are oxyethylene group (EO) or oxypropylene group (PO) modified bisphenol A (meth) acrylate compounds, polyalkylene glycol di (meth) acrylate compounds, and (EO) or (PO) modified tris. It is preferable to include at least one selected from the group consisting of methylolpropane tri (meth) acrylate compounds.

  Examples of the (EO) or (PO) modified bisphenol A-based (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxy) And polypropoxy) phenyl) propane.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxynonaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl ) Propane, 2,2-bis (4-((meth) acryloxide decaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyto) Decaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 ( Shin-Nakamura Chemical Co., Ltd., product name) is commercially available.

  Examples of the 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxyheptapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl ) Propane, 2,2-bis (4-((meth) acryloxide decapropoxy) phenyl) propane, 2,2-bis (4-((me ) Acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxyhexadecapropoxy) phenyl) propane, and the like.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane. 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. . These may be used alone or in combination of two or more.

  As the polyalkylene glycol di (meth) acrylate, for example, a compound represented by the following general formula (6), (7) or (8) is preferable.

［一般式（６）中、Ｒはそれぞれ独立に水素原子又はメチル基を示し、ＥＯはオキシエチレン基を示し、ＰＯはオキシプロピレン基を示し、ｒ^１＋ｒ^２＋ｓ^１は１１〜１００の整数である。］

[In General Formula (6), R independently represents a hydrogen atom or a methyl group, EO represents an oxyethylene group, PO represents an oxypropylene group, and r ¹ + r ² + s ¹ is an integer of 11 to 100. is there. ]

［一般式（７）中、Ｒはそれぞれ独立に水素原子又はメチル基を示す。ＥＯはオキシエチレン基を示し、ＰＯはオキシプロピレン基を示し、ｓ^２＋ｓ^３＋ｒ^３は、１１〜１００の整数である。］

[In General Formula (7), R represents a hydrogen atom or a methyl group each independently. EO represents an oxyethylene group, PO represents an oxypropylene group, and s ² + s ³ + r ³ is an integer of 11 to 100. ]

[In General Formula (8), R represents a hydrogen atom or a methyl group each independently. EO represents an oxyethylene group, PO represents an oxypropylene group, and r ⁴ + s ⁴ is an integer of 11 to 100. ]

  The total number of oxyethylene groups and oxypropylene groups in the general formulas (6), (7) and (8) is preferably 12 to 50, and 13 to 25 from the viewpoint of obtaining a cured film having lower elasticity. More preferably, it is more preferably 15-20.

Specific examples of the compound represented by the general formula (6) include a vinyl compound (Hitachi Chemical Co., Ltd.) in which R is a methyl group, r ¹ + r ² = 6 (average value), and s ¹ = 12 (average value). Kogyo Co., Ltd., trade name: FA-023M) and the like.

Specific examples of the compound represented by the general formula (7) include a vinyl compound (Hitachi Chemical Co., Ltd.) in which R is a methyl group, r ³ = 6 (average value), and s ² + s ³ = 12 (average value). Kogyo Co., Ltd., trade name: FA-024M) and the like.

  As the (EO) or (PO) modified trimethylolpropane tri (meth) acrylate compound, for example, a compound represented by the following general formula (9) is preferable.

［一般式（９）中、Ｒはそれぞれ独立に水素原子又はメチル基を示し、−（Ｏ−Ｂ）−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−Ｂ）−の繰り返し総数ｂ_１＋ｂ_２＋ｂ_３は、１１〜１００の整数である。］

[In general formula (9), R represents a hydrogen atom or a methyl group each independently,-(OB)-represents an oxyethylene group and / or an oxypropylene group, and-(OB)-is repeated. The total number b ₁ + b ₂ + b ₃ is an integer of 11 to 100. ]

Further, in the general formula (9), from the viewpoint of obtaining a cured film having lower elasticity, b ₁ + b ₂ + b ₃ is preferably 13 to 60, more preferably 15 to 50, and more preferably 18 to More preferably, it is 40.

  Specific examples of the compound represented by the general formula (9) include, for example, trimethylolpropane polyethoxytri (meth) acrylate, trimethylolpropane polypropoxytri (meth) acrylate, trimethylolpropane polyethoxypolypropoxytri ( And (meth) acrylate. Among the compounds represented by the general formula (9), for example, TMPT-21 (manufactured by Nippon Kayaku Co., Ltd.) is commercially available as trimethylolpropane triacrylate to which 21 mol of an oxyethylene group has been added.

  In addition to the components (B1) and (B2), the component (B) preferably contains (B3) a compound represented by the following general formula (1) from the viewpoint of improving resolution. .

［一般式（１）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 General Formula (1), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, a methyl group or a halogenated methyl group, R ⁵ represents an alkyl group having 1 to 6 carbon atoms, It represents either a halogen 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 (1) 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 them, γ-chloro-β-hydroxypropyl-β ′-(meth) Acryloyloxyethyl-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). These may be used alone or in combination of two or more.

  Moreover, it is preferable that (B) component contains the compound represented by following General formula (10) from the viewpoint which makes a resolution favorable. The compound represented by the general formula (10), 2-hydroxy-3-phenoxypropyl acrylate, is commercially available as NK ester 702A (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).

  From the viewpoint of the coating properties of the photosensitive resin composition and the mechanical strength of the photocured product, the content of the component (B) is based on 100 parts by mass of the total amount of the component (A) and the component (B). It is preferable to set it as 40-80 mass parts, and it is more preferable to set it as 45-70 mass parts.

  The content of the compound (B1) is preferably 20 to 95% by mass and more preferably 30 to 70% by mass with respect to 100 parts by mass of the total amount of the component (B). Moreover, it is preferable to set it as 5-80 mass% with respect to 100 mass parts of total amounts of (B) component, and, as for content of the said (B2) compound, it is more preferable to set it as 10-40 mass%.

  Examples of the photopolymerization initiator of the component (C) in the present invention include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-. Diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] Aromatic ketones such as 2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenyl Anthraquinone, 2,3-diphenylanthraquinone Quinones such as 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin Benzoin ether compounds such as ethyl ether and benzoin phenyl ether, benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) Acridine derivatives such as heptane, N-phenylglycine, N-phenylglycine derivatives, coumarin compounds, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5 − (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- ( p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like. Among these, from the viewpoint of improving the resolution, it is preferable to include both 1,7-bis (9,9′-acridinyl) heptane and 2,2-dimethoxy-1,2-diphenylethane-1-one. . Further, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound. Moreover, a combination of a thioxanthone compound and a tertiary amine compound may be used, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid. These are used alone or in combination of two or more.

  The content of the component (C) is preferably 0.1 to 20 parts by mass, and 0.2 to 10 parts by mass with respect to 100 parts by mass as a total of the components (A) and (B). It is more preferable. If this content is less than 0.1 parts by mass, the photosensitivity tends to be insufficient, and if it exceeds 20 parts by mass, the absorption at the surface of the composition increases during exposure and the internal photocuring is insufficient. Tend to be.

  Examples of the inorganic black pigment of component (D) used in the present invention include titanium black, carbon black, cobalt black and the like, and titanium black is preferably used from the viewpoint of suppressing fading during post-heating treatment.

  The content of the (D) inorganic black pigment is the total amount of the component (A) and the component (B) from the viewpoint of the light shielding property of the photosensitive resin composition, the dispersion stability, and the appearance of the coating film when forming the photosensitive element. It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts, and it is more preferable that it is 0.2-5 mass parts.

  If necessary, the photosensitive resin composition of the present invention further contains a dye such as malachite green, a photochromic agent such as tribromophenylsulfone or leucocrystal violet, a thermochromic inhibitor, or a plasticizer such as p-toluenesulfonamide. , Pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc., (A) component and (B ) Each component may be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total component. These may be used alone or in combination of two or more.

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

  The method for forming the photosensitive resin composition layer on the substrate of the 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. It can be applied and dried. 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. The thickness of the photosensitive resin composition layer to be applied varies depending on the use, but is preferably about 1 to 100 μm after drying. Examples of the protective film in the case where the protective film is used after being coated as a liquid resist include polymer films such as polyethylene and polypropylene.

  The photosensitive element of this invention is equipped with the support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on it.

  As the support, for example, a polyester film such as polyethylene terephthalate, or a polymer film such as polypropylene or polyethylene 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.

Although the formation method of the photosensitive resin composition layer on a support body is not specifically limited, It can implement preferably by apply | coating and drying the solution of the photosensitive resin composition. The thickness of the photosensitive resin composition layer to be applied varies depending on the use, but is preferably 1 to 100 μm after drying. When used as a partition wall of an image display device, the thickness of the photosensitive resin composition layer is more preferably 10 to 60 μm, and still more preferably 20 to 55 μm, after drying.
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 at 70 to 150 ° C. for about 5 to 30 minutes. Further, the amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  You may coat | cover the photosensitive resin composition layer surface using the said polymer film used as a support body as a protective film. As the protective film, those having a smaller adhesive force between the photosensitive resin composition layer and the protective film than the adhesive force between the photosensitive resin composition layer and the support are preferable, and a film having a low fish eye is preferable. Furthermore, the photosensitive film may have 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, the support, and any protective film. Good.

  The manufactured photosensitive element is usually wound around a cylindrical core and stored. In addition, it is preferable to wind up so that a support body may become an outer side at this time. 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. Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

  Next, a method for forming the partition wall of the image display device of the present invention will be described. That is, a lamination step of laminating a photosensitive resin composition layer using a photosensitive resin composition or a photosensitive element on a substrate of an image display device, and an actinic ray at a predetermined portion of the photosensitive resin composition layer An exposure step of irradiating and photocuring the exposed portion, and a developing step of removing a portion other than the exposed portion to form a photocured product pattern.

  First, the above-described photosensitive resin composition layer of the present invention is laminated on a substrate of an image display device. Examples of the substrate include an insulating substrate such as a glass substrate or a polymer substrate, a semiconductor substrate such as a silicon substrate, a semiconductor substrate on which an electrode such as ITO is formed, and a flexible substrate. Among them, a flexible substrate is preferably used because it has been attempted to make the image display apparatus flexible. As a lamination method, the above-described coating method is used, and a photosensitive element can also be used.

In the laminating method using the photosensitive element, when a protective film is present on the photosensitive resin composition layer, it is laminated on the substrate while removing the protective film. As the lamination condition, for example, by heating the photosensitive resin composition layer to about 70 to 130 ° C., pressure bonding is performed on the substrate at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ). The method of laminating etc. is mentioned, and it is also possible to laminate under reduced pressure. The shape of the substrate surface is usually flat, but irregularities and electrode patterns may be formed as necessary.

  After lamination of the photosensitive resin composition, the photosensitive resin composition layer is irradiated with an actinic ray in an image form to photocur the exposed portion. As a method of irradiating actinic rays in an image form, there is a method of setting a mask pattern on the photosensitive resin composition layer and irradiating the image form with an actinic ray and photocuring the photosensitive resin composition layer in the exposed portion. is there. The mask pattern may be a negative type or a positive type, and a commonly used one can be used. As the light source of actinic light, 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 a mask pattern can also be used.

  A photocured material pattern is formed on the substrate for an image display device by selectively removing the photosensitive resin composition layer in the unexposed portion after the exposure by development. In the development step, when a support is present, the support 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% sodium 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.

  As a treatment after development, the formed photocured product pattern may be further cured by a heat treatment at about 60 to 250 ° C., if necessary.

  The photosensitive resin composition of the present invention preferably has a tensile elastic modulus (25 ° C.) of 1 GPa or less at a film thickness of 45 μm of a cured film thermally cured at 120 ° C. for 1 hour. Thereby, the partition which can respond to a flexible substrate can be formed. A tensile modulus of 1 GPa or less can be achieved by using a large amount of highly flexible material for the component (A), the compound (B), particularly the compound (B2), or by reducing the crosslinking density. As the compound (B2) has a large number of repeating oxyethylene groups and / or oxypropylene groups, the elastic modulus tends to decrease.

  The method for producing an image display device of the present invention includes a step of filling a display medium such as particles in the partition obtained in the above step, a step of attaching a substrate to the opposite side of the partition so as to face one substrate, Have Examples of the substrate include an insulating substrate such as a glass substrate or a polymer substrate, a semiconductor substrate such as a silicon substrate, or a semiconductor substrate on which an electrode such as ITO is formed.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples without departing from the technical idea of the present invention.

The materials shown in Table 1 and Table 2 were mixed by stirring to obtain a solution of the photosensitive resin composition.
(Synthesis Example 1)
[Synthesis of Binder Polymer (a)]
To a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 500 g of a mixture of methyl cellosolve and toluene having a mass ratio of 3: 2 was added and stirred while blowing nitrogen gas, Heated to 85 ° C. On the other hand, 150 g of methacrylic acid as a polymerizable monomer, 110 g of methacrylic acid methyl ester, 65 g of acrylic acid ethyl ester, 50 g of butyl methacrylate, 125 g of styrene and 2.5 g of azobisisobutyronitrile (hereinafter referred to as “polymeric monomer”) The solution a was added dropwise to the above mixture of methyl cellosolve and toluene having a mass ratio of 3: 2 heated to 85 ° C. over 4 hours, and then stirred at 85 ° C. Incubated for 2 hours. Further, a solution prepared by dissolving 0.5 g of azobisisobutyronitrile in 150 g of a mixture of methyl cellosolve and toluene having a mass ratio of 3: 2 was dropped into the flask over 10 minutes. Mixing the acetone and propylene glycol monomethyl ether in a mass ratio of 3: 2 so that the solution after dripping is kept at 85 ° C. for 5 hours while stirring and then cooled to have a non-volatile content (solid content) of 43% by mass. Dilution with a solvent gave a binder polymer (a). The obtained binder polymer (a) had a weight average molecular weight of 50,000, a dispersity of 2.0, and an acid value of 195 mgKOH / g.

In addition, the weight average molecular weight of the binder polymer was measured by gel permeation chromatography, and was derived by conversion using a standard polystyrene calibration curve. The measurement conditions of gel permeation chromatography (GPC) are 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.)

配合量の単位：ｇ（固形分）

Unit of blending amount: g (solid content)

配合量の単位：ｇ（固形分）

Unit of blending amount: g (solid content)

The materials used in Tables 1 and 2 are shown below.
HT-9082-94: It consists of a photopolymerizable compound obtained by reacting a hydroxyl group-terminated polycarbonate compound, organic isocyanate and 2-hydroxyethyl acrylate, and has a weight average molecular weight of 4000 (trade name, Hitachi Chemical) Kogyo Co., Ltd., 75 mass% methyl ethyl ketone solution).
UF-TC-4-55: a photopolymerizable compound obtained by reacting a hydroxyl group-terminated polyester compound, organic isocyanate and 2-hydroxyethyl acrylate, and having a weight average molecular weight of 20000 (trade name, (Kyoeisha Chemical Co., Ltd., 60 mass% methyl ethyl ketone solution).
UF-8003M: a photopolymerizable compound obtained by reacting 2 mol of 2-hydroxyethyl acrylate with a urethane compound having an isocyanate group at the terminal, and having a weight average molecular weight of 3500 (trade name, Kyoeisha Chemical Co., Ltd.) Manufactured, 80 mass% methyl ethyl ketone solution).
UA-21EB: a compound in which R ¹ is the general formula (5) in the general formula (2), n = 6, m = 4, and R ² is a methyl group (Shin-Nakamura Chemical Co., Ltd., trade name)
BPE-1300: 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
FA-023M: In general formula (6), R is a methyl group, r ¹ + r ² = 6 (average value), s ¹ = 12 (average value) (product name, manufactured by Hitachi Chemical Co., Ltd.)
FA-024M: In general formula (7), R is a methyl group, r ³ = 6 (average value), s ² + s ³ = 12 (average value) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
TMPT-21: a compound in which R is a hydrogen atom and b1 + b2 + b3 = 21 (average value) in general formula (9) (manufactured by Nippon Kayaku Co., Ltd.)
FA-MECH: γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate (manufactured by Hitachi Chemical Co., Ltd., product name)
702A: 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
FA-321M: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (trade name, manufactured by Hitachi Chemical Co., Ltd.)
A-GLY-9E: glycerin nonaethoxytriacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name)
N-1717: 1,7-bis (N-acridinyl) heptane (manufactured by ADEKA Corporation)
Irgacure 651 (I-651): 2,2-dimethoxy-1,2-diphenylethane-1-one (product name, manufactured by Nagase Sangyo Co., Ltd.)
TPS: Tribromomethylphenylsulfone (manufactured by Sumitomo Seika Co., Ltd., product name)
EAB: N, N′-tetraethyl-4,4′-diaminobenzophenone (trade name, manufactured by Hodogaya Chemical Co., Ltd.)
Silane coupling agent: SZ-6030: methacryloyloxypropyltrimethoxysilane (product name, manufactured by Toray Dow Corning Co., Ltd.)
TLS: Toluene MAL: Methanol

  The solution of the photosensitive resin composition obtained in Table 1 was uniformly applied on a 16 μm-thick polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name: HTR-02), and hot air convection drying at 90 ° C. After drying for 10 minutes in a machine, the film is protected by a polyethylene protective film (tensile strength in the film longitudinal direction: 16 MPa, tensile strength in the film width direction: 12 MPa, trade name: NF-15, manufactured by Tamapoly Co., Ltd.). A sex element was obtained. The film thickness after drying of the photosensitive resin composition layer was 45 μm.

<Evaluation of light shielding properties>
The photosensitive element obtained as described above was cut out in a 20 cm square, and the photosensitive resin composition layer was visually observed from above the protective film. The results are shown in Tables 3 and 4.

  On the other hand, on the ITO surface of the PET substrate with ITO (manufactured by Toyobo Co., Ltd.), the photosensitive element was 110 ° C. while peeling the polyethylene protective film so that the photosensitive resin composition layer was in contact with the ITO surface. Laminate through a heated laminating roll. The structure of the obtained laminate is in the order of a PET substrate with ITO, a photosensitive resin composition layer, and a polyethylene terephthalate film. This laminate was evaluated for sensitivity, adhesion and resolution. The results are shown in Tables 3 and 4.

<Evaluation of sensitivity>
Using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd.) EXM-1201 having a high-pressure mercury lamp, a phototool having a 41-step tablet is brought into close contact with the laminated polyethylene terephthalate film, and the energy amount is 100 mJ / cm ² . 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 30 seconds to remove unexposed portions. The number of remaining steps after development of the 41-step tablet was determined, and this was defined as sensitivity (ST = x / 41). It shows that a sensitivity is so high that this value is large.

<Evaluation of adhesion>
Using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd.) EXM-1201 having a high-pressure mercury lamp, a wiring pattern having a line width / space width of 400/6 to 400/47 (unit: μm) as a negative for adhesion evaluation A phototool having a 41-step tablet and a phototool having a 41-step tablet were brought into close contact with the polyethylene terephthalate film of the laminate, and exposure was performed with an energy amount of 29.0 after development of the 41-step tablet. . 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 and evaluate the adhesion. Adhesion is expressed by the width (μm) of the line that remains without being peeled off by the developer. The smaller this value, the tighter the line is, without peeling from the PET substrate, Indicates high.

<Evaluation of resolution>
A phototool having a 41-step tablet and a phototool having a wiring pattern having a line width / space width of 400/6 to 400/47 (unit: μm) as a negative for resolution evaluation are closely adhered to the polyethylene terephthalate film of the laminate. Then, using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd.) EXM-1201 having a high-pressure mercury lamp 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 30 seconds to remove the unexposed portion and evaluate the resolution. The resolution is represented by the smallest space width (μm) in which the unexposed portion is well removed by the development processing, and the smaller the numerical value, the better the resolution.

<Evaluation of elastic modulus>
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. Then, 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 (made by Oak Manufacturing Co., Ltd.) EXM-1201 from the polyethylene terephthalate film of the said laminated body. In the exposure of the laminate, the energy amount was set such that the number of remaining step steps after development of the 41-step step tablet was 29.0. Furthermore, it developed by spraying 1 mass% sodium carbonate aqueous solution for 30 seconds at 30 degreeC. Next, ultraviolet irradiation (ultraviolet irradiation degree: ² J / cm ² ) was performed using an ultraviolet irradiation device (Toshiba Denshi Co., Ltd., rated voltage 200 V, rated power consumption 7.2 kW), and then the polyethylene terephthalate film was peeled off. It left still for 60 minutes in the box-type dryer (Mitsubishi Electric Corporation make, model number: NV50-CA) heated to 120 degreeC. The laminate after the heat treatment was cut into a width of 10 mm, the distance between chucks was 50 mm, and the tensile elastic modulus (25 ° C.) was determined at a constant speed of 2 cm / min.

As is apparent from Tables 2 and 3, Examples 1 to 8 have excellent light-shielding properties and sensitivity, and the cured film has sufficiently low elasticity, and is excellent in resolution and adhesion. is there.
On the other hand, Comparative Examples 1 to 3 having no component (B2) have a high elastic modulus.
In Examples 2 to 4 of the present invention, higher levels of resolution and adhesion than those in Examples 1 and 5 to 8 are obtained.

Claims (13)

A photosensitive resin composition for forming a partition wall of an image display device, the photosensitive resin composition comprising:
(A) a binder polymer having a carboxyl group,
(B) a photopolymerizable compound,
(C) a photopolymerization initiator and (D) an inorganic black pigment, and (B) the photopolymerizable compound,
(B1) a compound having an ethylenically unsaturated group and a urethane bond in the molecule;
(B2) a compound having an ethylenically unsaturated group and an oxyethylene group and / or an oxypropylene group in the molecule, wherein the total number of repeating oxyethylene groups and / or oxypropylene groups is 16 to 100;
A photosensitive resin composition comprising:   The photosensitive resin composition of Claim 1 in which the said (B1) component contains the compound which has an isocyanuric ring structure.   The photosensitive resin composition of Claim 1 or 2 in which the said (B1) component contains the compound of weight average molecular weight 2,000-10,000.   The component (B2) is an oxyethylene group (EO) or oxypropylene group (PO) modified bisphenol A (meth) acrylate compound, a polyalkylene glycol di (meth) acrylate compound, and an (EO) or (PO) modified The photosensitive resin composition in any one of Claims 1-3 containing at least 1 sort (s) chosen from the group which consists of a trimethylol propane tri (meth) acrylate compound. The photosensitive resin composition in any one of Claims 1-4 in which the said (B) component further contains the compound represented by (B3) following General formula (1).

[In General Formula (1), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, a methyl group or a halogenated methyl group, R ⁵ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, Any one of a hydroxyl group is shown, p shows the integer of 0-4. 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. ]   The photosensitive resin composition according to claim 1, wherein the (D) inorganic black pigment contains titanium black.   The photosensitive resin composition according to any one of claims 1 to 6, wherein a tensile elastic modulus at a film thickness of 45 µm of a cured film thermally cured at 120 ° C for 1 hour is 1 GPa or less.   A photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition in any one of Claims 1-7 formed on this support body. The photosensitive element of Claim 8 whose film thickness of the said photosensitive resin composition layer is 1-100 micrometers. A laminating step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 7 on a substrate of an 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 to form a photocured product pattern;
A method for forming a partition wall of an image display device.   A method for forming a partition wall of an image display device, further comprising a heating step of heat-curing the photocured product pattern formed by the method for forming a partition wall of the image display device according to claim 10 at 60 to 250 ° C.   The method for forming a partition wall of an image display device according to claim 10 or 11, wherein the substrate is a flexible substrate. Filling the display medium into the partition formed by the partition forming method of the image display device according to any one of claims 10 to 12,
A step of attaching the substrate to the opposite side of the partition so as to face one of the substrates;
A method for manufacturing an image display device.