Photosensitive element, photosensitive element roll, method for producing resist pattern, and electronic component
09971244 ยท 2018-05-15
Assignee
Inventors
- Naoki Sasahara (Tokyo, JP)
- Ikuo Mukai (Tokyo, JP)
- Mayumi Sato (Tokyo, JP)
- Yasuhiro Seri (Tokyo, JP)
- Koji Abe (Tokyo, JP)
- Manami Kiryu (Tokyo, JP)
Cpc classification
G03F7/161
PHYSICS
H05K2203/066
ELECTRICITY
G03F7/027
PHYSICS
G03F7/11
PHYSICS
G03F7/343
PHYSICS
H05K3/0079
ELECTRICITY
G06F2203/04103
PHYSICS
International classification
G03F7/11
PHYSICS
B32B37/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A photosensitive element 1 comprises a support film 10, a protective film (polypropylene film) 30, and a photosensitive layer 20 which is arranged between the support film 10 and the protective film 30, wherein the protective film 30 has a principal surface 30a at a side of the photosensitive layer 20 and a principal surface 30b at an opposite side of the principal surface 30a, and the principal surface 30a and the principal surface 30b are smooth.
Claims
1. A photosensitive element, comprising: a support film; a polypropylene film; and a photosensitive layer arranged between the support film and the polypropylene film, wherein the polypropylene film has a first surface at a side of the photosensitive layer and a second surface at an opposite side to the first surface, and an arithmetic mean roughness Ra of the first surface and the second surface is 0.05 m or less.
2. A photosensitive element, comprising: a support film; a polypropylene film; and a photosensitive layer arranged between the support film and the polypropylene film, wherein the polypropylene film has a first surface at a side of the photosensitive layer and a second surface at an opposite side to the first surface, and a maximum height Rmax of the first surface and the second surface is 0.5 m or less.
3. The photosensitive element according to claim 1, wherein a thickness of the photosensitive layer is less than 20 m.
4. The photosensitive element according to claim 1, wherein a thickness of the photosensitive layer is 10 m or less.
5. The photosensitive element according to claim 1, wherein an average light transmittance is 80% or more in a wavelength region of 400 to 700 nm.
6. The photosensitive element according to claim 1, wherein the photosensitive layer contains a binder polymer, a photopolymerizable compound and a photopolymerization initiator.
7. A method for producing a cured product, comprising: a step of peeling the polypropylene film of the photosensitive element according to claim 1; and then laminating the photosensitive layer and the support film on a base material; and a step of irradiating the photosensitive layer with an active ray to form a photo-cured portion.
8. A photosensitive element roll, comprising: a core, and a photosensitive element which is wound around the core, wherein the photosensitive element is the photosensitive element according to claim 1.
9. A method for producing a resist pattern, comprising: a step of peeling the polypropylene film of the photosensitive element according to claim 1, and then laminating the photosensitive layer and the support film on a base material; a step of irradiating a predetermined portion of the photosensitive layer with an active ray to form a photo-cured portion; and a step of removing a portion other than the photo-cured portion in the photosensitive layer.
10. An electronic component, comprising a resist pattern obtained by the method for producing the resist pattern according to claim 9.
11. The photosensitive element according to claim 2, wherein a thickness of the photosensitive layer is less than 20 m.
12. The photosensitive element according to claim 2, wherein a thickness of the photosensitive layer is 10 m or less.
13. The photosensitive element according to claim 2, wherein an average light transmittance is 80% or more in a wavelength region of 400 to 700 nm.
14. The photosensitive element according to claim 2, wherein the photosensitive layer contains a binder polymer, a photopolymerizable compound and a photopolymerization initiator.
15. A method for producing a cured product, comprising: a step of peeling the polypropylene film of the photosensitive element according to claim 2; and then laminating the photosensitive layer and the support film on a base material; and a step of irradiating the photosensitive layer with an active ray to form a photo-cured portion.
16. A photosensitive element roll, comprising: a core, and a photosensitive element which is wound around the core, wherein the photosensitive element is the photosensitive element according to claim 2.
17. A method for producing a resist pattern, comprising: a step of peeling the polypropylene film of the photosensitive element according to claim 2, and then laminating the photosensitive layer and the support film on a base material; a step of irradiating a predetermined portion of the photosensitive layer with an active ray to form a photo-cured portion; and a step of removing a portion other than the photo-cured portion in the photosensitive layer.
18. An electronic component, comprising a resist pattern obtained by the method for producing the resist pattern according to claim 17.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
(18) Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments, but various changes can be made within a range of the scope.
(19) In the present specification, (meth)acrylic acid means acrylic acid or methacrylic acid, (meth)acrylate means acrylate or methacrylate, and (meth)acrylic resin means an acrylic resin or a methacrylic resin.
(20) (Photosensitive Element)
(21) The photosensitive element according to the present embodiment has a support film, a polypropylene film, and a photosensitive layer which is arranged between the support film and the polypropylene film, wherein the polypropylene film has a first surface at the side of the photosensitive layer and a second surface at the opposite side to the first surface, and at least one of the followings (I) to (III) is satisfied.
(22) (I) The first surface and the second surface are smooth.
(23) (II) The arithmetic mean roughness Ra of the first surface and the second surface is 0.05 m or less.
(24) (III) The maximum height Rmax of the first surface and the second surface is 0.5 m or less.
(25) The photosensitive element according to the present embodiment will be further described below.
(26) The support film 10 can employ a polymer film, and is preferably a polymer film having heat resistance and solvent resistance. Examples of such a polymer film include: polyester films such as a polyethylene terephthalate film; polyolefin films such as a polyethylene film and a polypropylene film; and polycarbonate films. Among these, the polyethylene terephthalate film is preferable, from the viewpoint of being excellent in transparency and heat resistance.
(27) Examples of the support film 10 include: Tetron (brand name) film G2 series, HS series, 03 series, and Mylar film D series made by Teijin DuPont Films Japan Limited; Lumirror FB50 series made by Toray Industries, Inc.; and Cosmo Shine series made by TOYOBO CO., LTD.
(28) The thickness of the support film 10 is preferably 1 m or more, and more preferably 12 m or more, from the viewpoint of suppressing the occurrence of such a problem that the support film is broken at the time of coating, by suppressing the lowering of the mechanical strength. The thickness of the support film 10 is preferably 100 m or less, and more preferably 25 m or less, from the viewpoint of suppressing the lowering of the resolution and also suppressing a rise in the price.
(29) The photosensitive layer 20 contains a photosensitive resin composition. The photosensitive resin composition is not limited in particular as long as it has photosensitivity, but the examples include compositions which contain (a) a binder polymer, (b) a photopolymerizable compound and (c) a photopolymerization initiator.
(30) Examples of the (a) component include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins and phenol resins. The (a) component can be used solely or in combination with other one or more types. Among these, the (a) component is preferably (meth)acrylic resins, from the viewpoint of being excellent in alkali development properties. The (a) component has, for instance, a constitutional unit derived from a photopolymerizable monomer, and can be produced by subjecting the photopolymerizable monomer to polymerization (for instance, radical polymerization).
(31) Examples of the photopolymerizable monomers include: styrene and polymerizable styrene derivatives in which an -site or an aromatic ring is substituted such as vinyltoluene; (meth)acrylic acid; alkyl (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; (meth)acrylic acid derivatives such as dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylic acid ester, dimethylaminoethyl (meth)acrylic acid ester, diethylaminoethyl (meth)acrylic acid ester and glycidyl (meth)acrylic acid ester; and maleic acid. The photopolymerizable monomers can be used solely or in combination with other one or more types.
(32) The (a) component preferably contains at least one selected from among (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate and glycidyl (meth)acrylic acid ester, as the above described photopolymerizable monomer, from the viewpoint of being excellent in flexibility.
(33) Examples of the polymerization initiators for polymerizing the photopolymerizable monomer include radical polymerization initiators. Polymerization initiators which are used for a reversible addition fragmentation chain transfer polymerization (RAFT polymerization) can be appropriately used as the radical polymerization initiator.
(34) Examples of the radical polymerization initiators include: peroxide initiators such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and dicumyl peroxide; and azo initiators such as AIBN (2,2-azobisisobutyronitrile) and V-65 (azobisdimethylvaleronitrile). Among these, the azo initiators are preferable and the AIBN is more preferable, from the viewpoint of being capable of using a solvent with a low boiling point, resisting causing a side reaction, and the like.
(35) The weight average molecular weight of the (a) component is preferably 10000 or more, more preferably 15000 or more, further preferably 20000 or more, and particularly preferably 30000 or more, from the viewpoint of being excellent in resolution. The weight average molecular weight of the (a) component is preferably 200000 or less, more preferably 150000 or less, and further preferably 100000 or less, from the viewpoint of being excellent in the resolution. The weight average molecular weight of the (a) component can be measured by a gel permeation chromatography method (GPC) on the following conditions with the use of a calibration curve of standard polystyrene.
(36) [GPC Condition]
(37) Pump: Hitachi L-6000 type (made by Hitachi, Ltd., product name)
(38) Column: Gelpack GL-R420, Gelpack GL-R430, and Gelpack GL-R440 (all made by Hitachi Chemical Co., Ltd., product names)
(39) Eluent: tetrahydrofuran
(40) Measurement temperature: 40 C.
(41) Flow rate: 2.05 mL/minute
(42) Detector: Hitachi L-3300 type RI (made by Hitachi, Ltd., product name)
(43) Photopolymerizable compounds having an ethylenic unsaturated group can be used as the photopolymerizable compound which is the (b) component. Examples of the photopolymerizable compounds having the ethylenic unsaturated group include monofunctional vinyl monomers, difunctional vinyl monomers, and polyfunctional vinyl monomers having at least three photopolymerizable ethylenic unsaturated groups. The (b) components can be used solely or in combination with other one or more types.
(44) Examples of the monofunctional vinyl monomers include the above described photopolymerizable monomers. Among these, (meth)acrylic acid, alkyl (meth)acrylic acid esters, benzyl (meth)acrylate and glycidyl (meth)acrylic acid ester are preferable.
(45) Examples of the difunctional vinyl monomers include polyethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2-bis(4-(meth)acryloxy polyethoxy phenyl) propane), 2,2-bis(4-((meth)acryloxy polypropoxy)phenyl) propane, 2,2-bis(4-((meth)acryloxy polyethoxy polypropoxy)phenyl) propane, and bisphenol A diglycidyl ether di(meth)acrylate.
(46) Examples of the polyfunctional vinyl monomers having at least three photopolymerizable ethylenic unsaturated groups include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and trimethylolpropane triglycidyl ether tri(meth)acrylate.
(47) The (b) component preferably contains the polyfunctional vinyl monomer having at least three photopolymerizable ethylenic unsaturated groups, from the viewpoint of being excellent in adhesiveness with the base material (for instance, transparent base material) when the cured product is formed on the base material.
(48) Examples of the photopolymerization initiators which are the (c) component include:
(49) aromatic ketones such as benzophenone, N,N,N,N-tetramethyl-4,4-diaminobenzophenone (also known as Michler's ketone), 4-methoxy-4-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone;
(50) benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether;
(51) benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin;
(52) oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime);
(53) phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide;
(54) benzyl derivatives such as benzyl dimethyl ketal;
(55) acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9-acridinyl)heptane; and
(56) N-phenylglycine, N-phenylglycine derivatives, coumarin-based compounds and oxazol-based compounds.
(57) Among these, the oxime ester compound and the phosphine oxide compound are preferable, from the viewpoint of being excellent in transparency of the cured product (protective film and the like) to be formed, and being excellent in pattern forming capability (for instance, pattern forming capability at the time when thickness is 10 m or less). The (c) components can be used solely or in combination with other one or more types.
(58) The amount of the (a) component to be blended in the photosensitive layer 20 is preferably 40 parts by mass or more, and more preferably 50 parts by mass or more, with respect to 100 parts by mass of the total of the (a) component and the (b) component, from the viewpoint of being excellent in coating film properties, and suppressing edge fusion (phenomenon that resin bleeds from end of photosensitive element). The amount of the (a) component to be blended is preferably 80 parts by mass or less, and more preferably 70 parts by mass or less, with respect to 100 parts by mass of the total of the (a) component and the (b) component, from the viewpoint of suppressing the lowering of sensitivity and also suppressing the decrease of a mechanical strength.
(59) The amount of the (b) component to be blended in the photosensitive layer 20 is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more, with respect to 100 parts by mass of the total of the (a) component and the (b) component, from the viewpoint of enhancing a mechanical strength of the cured product (for instance, cured film). The amount of the (b) component to be blended is preferably 60 parts by mass or less, and more preferably 50 parts by mass or less, with respect to 100 parts by mass of the total of the (a) component and the (b) component, from the viewpoint of being excellent in coating film properties and suppressing the edge fusion (phenomenon that resin bleeds from end of photosensitive element).
(60) The amount of the (c) component to be blended in the photosensitive layer 20 is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, with respect to 100 parts by mass of the total of the (a) component and the (b) component, from the viewpoint that sufficient sensitivity is obtained. The amount of the (c) component to be blended is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, with respect to 100 parts by mass of the total of the (a) component and the (b) component, from the viewpoint of suppressing a phenomenon that absorption on the surface of the composition increases at the time of light exposure, and that the photocuring of the inner part becomes insufficient.
(61) The photosensitive layer 20 may contain: dyes such as malachite green; photochromic agents such as tribromomethylphenylsulfone and leuco crystal violet; plasticizers such as p-toluenesulfonamide; and polymerization inhibitors, heat coloring inhibitors, pigments, fillers, antifoaming agents, fire retardants, stabilizers, adhesiveness-imparting agents, leveling agents, peeling promoters, oxidation inhibitors, perfumes, imaging agents and heat crosslinking agents, as arbitrary components, as needed. The content of each of the arbitrary components is, for instance, 0.01 to 20 parts by mass, with respect to 100 parts by mass of the total of the (a) component and the (b) component. The above described arbitrary components can be used solely or in combination with other one or more types.
(62) The photosensitive layer 20 can be formed by: obtaining a solution having approximately 30 to 60 mass % of the solid content by dissolving the constituent in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ester, propylene glycol monomethyl ether acetate and dimethylacetamide or in a mixed solvent thereof; applying the solution onto the support film 10; and then drying the applied solution. Subsequently, on the photosensitive layer 20, the protective film 30 is laminated, and thereby the photosensitive element 1 is obtained.
(63) The thickness (thickness after drying) of the photosensitive layer 20 is preferably less than 20 m. In addition, the thickness of the photosensitive layer 20 is preferably the following thickness, from the viewpoint that an effect for suppressing the occurrence of the air bubble becomes easily obtained. Specifically, the thickness of the photosensitive layer 20 is preferably 1 m or more, and more preferably 2 m or more, from the viewpoint of suppressing the lowering of followability and suppressing the occurrence of a defect. The thickness of the photosensitive layer 20 is more preferably 15 m or less, further preferably 10 m or less, particularly preferably 9 m or less, extremely preferably 8 m or less, and very preferably 7 m or less, from the viewpoint that the electronic component is easily thinned (for instance, in the case where it is used as structural member of electronic component such as touch panel which is strongly demanded to be thinned, electronic component is easily thinned). Incidentally, the thickness of the photosensitive layer 20 may also be 20 m or more.
(64) The viscosity of the photosensitive layer 20 at 30 C. is preferably 15 MP.Math.s or more, and more preferably 25 MPa.Math.s or more, from the viewpoint of suppressing the occurrence of edge fusion when the photosensitive element is wound around the core. The viscosity of the photosensitive layer 20 at 30 C. is preferably 50 MP.Math.s or less, and more preferably 40 MPa.Math.s or less, from the viewpoint that the lowering of resin fluidization is suppressed, and the occurrence of the air void becomes easily suppressed.
(65) The protective film 30 is a polypropylene film. The protective film 30 has a principal surface (first surface) 30a at a side of the photosensitive layer 20, and a principal surface (second surface) 30b at an opposite side to the principal surface 30a, and the principal surface 30a and the principal surface 30b are smooth (both of surfaces are smooth).
(66) The state that both of the principal surface 30a and the principal surface 30b are smooth can be checked by winding the photosensitive element 1 around the core, and then laminating the photosensitive layer 20. In the case where the principal surface 30a and the principal surface 30b have unevenness and are not smooth, the unevenness is transferred onto the photosensitive layer 20 and the air bubble is formed; but in the case where both of the principal surface 30a and the principal surface 30b are smooth, the unevenness is not transferred onto the photosensitive layer 20 and accordingly the formation of the air bubble is suppressed.
(67) It can be checked whether both of the principal surface 30a and the principal surface 30b are smooth, by the following procedures. Firstly, the photosensitive element 1 is wound around the core (for instance, outer diameter of 84 mm and inner diameter of 76 mm) The photosensitive element 1 is wound around the core so that the support film 10 is arranged at the most outer side, for instance, with a tension of 90 N/m. Next, after the protective film 30 of the wound photosensitive element 1 has been peeled, a laminated product of the support film 10 and the photosensitive layer 20 (reference numeral F1 in
(68) An arithmetic mean roughness (Ra) of the principal surface 30a and the principal surface 30b is preferably 0.05 m or less, more preferably 0.04 m or less, further preferably 0.03 m or less, and particularly preferably 0.02 m or less, from the viewpoint of further suppressing the occurrence of the air bubble at the time of the lamination. The arithmetic mean roughness (Ra) may be 0 m.
(69) The maximum height (Rmax) of the principal surface 30a and the principal surface 30b is preferably 0.5 m or less, more preferably 0.4 m or less, and further preferably 0.35 m or less, from the viewpoint of further suppressing the occurrence of the air bubble at the time of the lamination. The maximum height (Rmax) may be 0 m.
(70) The arithmetic mean roughness (Ra) and the maximum height (Rmax) of both of the surfaces of the protective film 30 can be measured, for instance, by the following procedures.
(71) (a) A sample to be measured having a size of 5 cm10 cm is cut out from the protective film.
(72) (b) After one drop of water has been dripped on a flat glass substrate (10 cm10 cm) with a dropping pipette, the sample to be measured is brought into pressure contact with the glass substrate so that the air bubble does not enter, with a clean roller.
(73) (c) Both of the ends in the longitudinal direction of the sample to be measured are fixed by weights, and ten portions of measurement regions (region of 284.1 m213.1 m) in the sample to be measured are arbitrarily selected.
(74) (d) After the measurement regions are observed with a 50-times object lens with the use of the shape measuring laser microscope (VK-X200, made by KEYENCE CORPORATION), and also the arithmetic mean roughness (Ra) and the maximum height (Rmax) have been measured, the average value of the total 10 portions is calculated.
(75) (e) The above described steps (a) to (d) are repeated, and the measurement values are acquired three times in total; and the average value of the repeated three times is adopted as the arithmetic mean roughness (Ra) and the maximum height (Rmax).
(76) The thickness of the protective film 30 is preferably 1 m or more, more preferably 5 m or more, and further preferably 15 m or more so that a sufficient strength of the protective film 30 is obtained, from the viewpoint of suppressing being ruptured when the protective film 30 is laminated on the photosensitive layer 20. The thickness of the protective film 30 is preferably 100 m or less, more preferably 50 m or less, further preferably 35 m or less, and particularly preferably 30 m or less, from the viewpoint of suppressing a rise in the price and also suppressing the occurrence of a wrinkle at the time when the protective film 30 is laminated.
(77) Examples of the protective film 30 include E-201F (made by Oji F-Tex Co., Ltd., double-sided smooth polypropylene film).
(78) An adhesive strength between the photosensitive layer 20 and the support film 10 is preferably larger than an adhesive strength between the photosensitive layer 20 and the protective film 30. If the adhesive strength between the photosensitive layer 20 and the support film 10 is not smaller than the adhesive strength between the photosensitive layer 20 and the protective film 30, the photosensitive layer 20 tends to be transferred onto the side of the protective film 30, when the protective film 30 is removed at the time of the lamination.
(79) The photosensitive element 1 can be obtained, for instance, by applying the above described photosensitive resin composition onto the support film 10 and drying to form the photosensitive layer 20, and then by laminating the protective film 30 on the photosensitive layer 20.
(80) The average light transmittance of the photosensitive element 1 in a wavelength region of 400 to 700 nm is preferably 80% or more, and more preferably 85% or more, from the viewpoint that the photosensitive element can be preferably used for an application for a touch panel to which transparency is required, and the like. The light transmittance can be measured with a UV spectrometer (for instance, 228A type W beam spectrophotometer and ultraviolet and visible spectrophotometer (U-3310) made by Hitachi, Ltd.), a turbidity meter (for instance, NDH5000 which is product name and is made by NIPPON DENSHOKU INDUSTRIES Co., LTD.), and the like.
(81) The thickness of the photosensitive element 1 is preferably 20 m or more, and more preferably 30 m or more, from the viewpoint of further suppressing the occurrence of the air bubble in laminate. The upper limit of the thickness of the photosensitive element 1 is, for instance, 100 m.
(82) In the photosensitive element 1, the photosensitive layer 20 may come in contact with the support film 10 and/or the protective film 30. On the other hand, in the photosensitive element according to the present embodiment, another layer (intermediate layer) may be laminated in between the support film 10 and the protective film 30, in addition to the photosensitive layer 20, and the photosensitive layer 20 does not need to come in contact with the support film 10 or the protective film 30. For instance, the photosensitive element (photosensitive electroconductive film) 1a shown in
(83) The photosensitive element according to the present embodiment can be used for forming the cured product (which is particularly permanent resist such as insulating film, spacer, protective member of touch panel and the like, and for instance, is cured film composed of cured film pattern of photosensitive resin composition). The photosensitive element according to the present embodiment can be used for manufacturing an electronic component. For instance, the photosensitive element according to the present embodiment can be used for forming the cured product of the electronic component having the cured product (protective member and the like). The photosensitive element according to the present embodiment can be used for forming the cured product (for instance, resist pattern such as resin cured product pattern) on a base material (for instance, transparent base material). The photosensitive element according to the present embodiment can be used for manufacturing the touch panel. For instance, the photosensitive element according to the present embodiment can be used for forming the protective film (for instance, resist pattern such as resin cured product pattern) on the base material for the touch panel.
(84) (Photosensitive Element Roll)
(85) The photosensitive element 1 may be stored in any form, but can be usually stored in a form of being wound in a rolled form around a core having a cylindrical shape or the like. The photosensitive element roll according to the present embodiment includes the core, and the photosensitive element which is wound around the core, wherein the photosensitive element is the photosensitive element according to the present embodiment. The material of the core is not limited in particular as long as the material is conventionally used, and the examples include plastics such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, and an ABS resin (acrylonitrile-butadiene-styrene copolymer). When being stored, it is preferably wound so that the support film becomes the most outer side. An end face separator is preferably provided on an end face of the photosensitive element roll which is prepared by winding the photosensitive element in the rolled form, from the viewpoint of protecting the end face. In addition, a moisture-proof end face separator is preferably provided on the end face of the photosensitive element roll, from the viewpoint of edge fusion resistance. When being packed, the photosensitive element roll is preferably packed in a form of being wrapped with a black sheet having small moisture permeability.
(86) (Method for Producing Resist Pattern)
(87) The method for producing (forming) the resist pattern according to the present embodiment includes a lamination step, a light exposure step and a development step, in this order. The method using the photosensitive element 1 will be described below, as one example.
(88) In the lamination step, the protective film 30 of the photosensitive element 1 is peeled, and then the photosensitive layer 20 and the support film 10 are laminated on a base material (substrate or the like). The photosensitive layer 20 and the support film 10 are laminated on the base material so that the photosensitive layer 20 and the support film 10 are arranged on the base material in this order.
(89) The materials of the surface of the base material (uneven surface) on which the photosensitive element 1 is laminated are not limited in particular, but include, for instance, glass, silicon and metal.
(90) The heating temperature of the photosensitive layer 20 in the lamination step is preferably 50 to 130 C., and more preferably 90 to 130 C. A pressure-bonding pressure (roll linear pressure) is preferably 0.1 to 1.0 MPa (1 to 10 kgf/cm.sup.2). However, the heating temperature and the pressure-bonding pressure are not limited to the above described conditions. When the photosensitive layer 20 is heated to 50 to 130 C. as in the above description, the base material having the fine uneven structure does not necessarily need to be subjected to preheating treatment beforehand, but the base material can also be subjected to the preheating treatment so as to further enhance lamination properties.
(91) In the light exposure step, a predetermined portion of the photosensitive layer 20 is irradiated with active rays to form a photo-cured portion on the photosensitive layer 20. When the support film 10 is transparent which exists on the photosensitive layer 20, the photosensitive layer 20 may be irradiated with the active rays through the support film 10. When the support film 10 is opaque, the support film 10 is removed. The support film 10 is preferably transparent, from the viewpoint of protecting the photosensitive layer 20.
(92) A known light source (for instance, light source which effectively emits ultraviolet rays, such as carbon arc lamp, mercury vapor arc lamp, ultrahigh pressure mercury lamp, high pressure mercury lamp and xenon lamp) is used as the light source of the active rays. In addition to the above, a light source which effectively emits visible light such as a flood electric bulb for photography and a solar lamp can also be used.
(93) In the development step, a portion other than the photo-cured portion in the photosensitive layer 20 is removed to obtain the resist pattern. In the development step, after the light exposure step, the support film 10 is removed, as needed. The peeling step is generally performed by hands, but can be efficiently processed by using some jig or machine.
(94) The resist pattern may be further cured by being subjected to a heating treatment of approximately 80 to 250 C., as needed. The heating treatment may be performed before the support film 10 is peeled from the photosensitive layer 20, or may be performed after the support film 10 has been peeled from the photosensitive layer 20.
(95) (Electronic Component and Method for Manufacturing the Same)
(96) An electronic component according to the present embodiment comprises a cured product (cured film or the like) of the photosensitive layer of the photosensitive element according to the present embodiment. The electronic component comprises the above described cured product, for instance, as a protective member (protective film or the like). The electronic component according to the present embodiment comprises, for instance, the resist pattern which is obtained by the above described method for producing the resist pattern. Examples of the electronic component include a touch panel, a liquid crystal display, organic electroluminescence, a solar cell module, a printed wiring board, and electronic paper. The electronic component which is obtained by using the photosensitive element and the method for manufacturing the same (example of use of resist pattern, and portion of use of protective film) will be further described below.
(97) One example of the touch panel and the method for manufacturing the same will be described below with reference to
(98) Firstly, as is shown in
(99) Next, one example of a touch panel and a method for manufacturing the same will be described below with reference to
(100) The touch panel (electrostatic capacity type touch panel) 400 shown in
(101) On the transparent substrate 401, drawing wires 405 are arranged for transmitting a detected signal at the touched position, which has been detected by the transparent electrodes 403 and 404, to an external circuit. The drawing wire 405 and the transparent electrodes 403 and 404 are directly connected, and are also connected through the connection electrode 406 which are arranged on the transparent electrodes 403 and 404 (see
(102) On the drawing wire 405, the connection electrode 406 and the connection terminal 407, a protective film (resin cured film pattern) 422 is arranged. In the cross section shown in
(103) In addition, such a protective film 422 can also simultaneously protect an electrode in a sensing region. For instance, in
(104) A method for manufacturing the touch panel 400 using the photosensitive element according to the present embodiment will be described below. Firstly, on the transparent substrate 401, the transparent electrode 403 for detecting the X position coordinate is formed. Subsequently, the transparent electrode 404 for detecting the Y position coordinate is formed through an insulating layer (not shown). For instance, a method for etching a transparent electrode layer which is arranged on the transparent substrate 401 can be used as a method for forming the transparent electrodes 403 and 404.
(105) Next, on the transparent substrate 401, the drawing wire 405 for being connected to the external circuit, and the connection electrode 406 for connecting the drawing wire 405 with the transparent electrodes 403 and 404 therethrough are formed. The drawing wire 405 and the connection electrode 406 may be formed after the transparent electrodes 403 and 404 have been formed, or may also be simultaneously formed when the transparent electrodes 403 and 404 are formed. A method of etching after metal sputtering, for instance, can be used as a method for forming the drawing wire 405 and the connection electrode 406. The drawing wire 405 can be simultaneously formed when the connection electrode 406 is formed, for instance, by a screen printing method with the use of an electroconductive paste material containing flake-shaped silver. Next, the connection terminal 407 is formed for connecting the drawing wire 405 with the external circuit.
(106) The photosensitive layer of the photosensitive element according to the present embodiment is pressure-bonded so as to cover the transparent electrode 403, the transparent electrode 404, the drawing wire 405, the connection electrode 406 and the connection terminal 407 which have been formed according to the above described steps, to transfer the photosensitive layer 20 onto these structural members. Next, the photosensitive layer 20 is irradiated with active rays in a patterned form through a photomask having a desired shape to form a photo-cured portion. After the irradiation with the active rays, development is performed to remove a portion other than the photo-cured portion in the photosensitive layer 20. Thereby, the protective film 422 which is composed of the photo-cured portion of the photosensitive layer 20 is formed. The touch panel provided with the protective film 422 (touch panel having base material for touch panel, which is provided with the protective film 422) 400 can be manufactured according to the above.
(107) Next, one example of an electrostatic capacity type touch panel in which the transparent electrodes exist on the same plane and a method for manufacturing the same will be described below with reference to
(108) The touch panel (electrostatic capacity type touch panel) 500 shown in
(109) A method for manufacturing the touch panel 500 will be described below with reference to
(110) The transparent electrodes 503 and 504 may be formed, for instance, according to a known method using ITO or the like. The drawing wires 505a and 505b can be formed according to a known method using metal such as Cu and Ag, in addition to the transparent electroconductive material. In addition, in the method for manufacturing the touch panel 500, a substrate may be used in which the drawing wires 505a and 505b are formed beforehand.
(111) Next, one example of a touch panel will be described below with reference to
(112) The touch panel 600 has a transparent substrate (transparent base material, base material for touch panel) 601, a transparent electrode 604, a wire (transparent electrode wire) 604a, a drawing wire 605, and an insulating film (insulating film, for instance, transparent insulating film) 625. The transparent electrode 604 and the wire 604a are arranged on the transparent substrate 601. The wire 604a extends from the transparent electrode 604. The insulating film 625 is arranged on the end of the transparent electrode 604 and the wire 604a. The drawing wire 605 is arranged on the insulating film 625. An opening 608 is formed in the insulating film 625 on the upside of the end of a part of the transparent electrodes 604. The transparent electrode 604 and the drawing wire 605 are connected and conducted to each other through the opening 608. The photosensitive element according to the present embodiment can be preferably used for forming the cured product (resin cured film pattern) as the insulating film 625.
EXAMPLES
(113) The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples.
(114) <Preparation of Solution of Photosensitive Resin Composition>
(115) A binder polymer solution was prepared in the following way. Firstly, a component (1) shown in Table 1 was charged into a flask which is provided with a stirrer, a reflux cooler, an inert gas introduction port and a thermometer, and the temperature was raised to 80 C. under a nitrogen gas atmosphere. A component (2) shown in Table 1 was uniformly dripped for 4 hours while a reaction temperature was kept at 80 C.2 C. After the component (2) was dripped, stirring was continued at 80 C.2 C. for 6 hours, and thereby the binder polymer solution (45 mass % of solid content) was obtained of which the weight average molecular weight (Mw) was approximately 80000.
(116) TABLE-US-00001 TABLE 1 Blending amount Component (parts by mass) (1) Propylene glycol monomethyl ether 62 Toluene 62 (2) Methacrylic acid 12 Methyl methacrylate 58 Ethyl acrylate 30 2,2-azobisisobutyronitrile 1.2
(117) Incidentally, the weight average molecular weight was obtained by measurement with a gel permeation chromatography method (GPC method) on the following conditions, and conversion with the use of a calibration curve of standard polystyrene.
(118) [GPC Conditions]
(119) Pump: Hitachi L-6000 type (product name, made by Hitachi, Ltd.)
(120) Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (all product names made by Hitachi Chemical Co., Ltd.)
(121) Eluent: tetrahydrofuran
(122) Measurement temperature: 40 C.
(123) Flow rate: 2.05 mL/minute
(124) Detector: Hitachi L-3300 type RI (product name, made by Hitachi, Ltd.)
(125) Each component shown in the following table 2 was mixed in a blending amount (of which unit is parts by mass) shown in Table 2, and thereby the solution of the photosensitive resin composition was prepared. Incidentally, the binder polymer solution which was synthesized in the above description was mixed so that a mass (solid content) of a nonvolatile content in the (a) component became the blending amount shown in Table 2.
(126) TABLE-US-00002 TABLE 2 Blending amount Constituent of photosensitive layer (parts by mass) (a) Binder polymer PM-300 60 (b) Photopolymerizable compound TMPTA 40 (c) Photopolymerization initiator OXE-01 2.5 Other components AW-500 0.1 SH-30 0.07
(127) The details of each of the components in Table 2 are as follows.
(128) (a) Binder polymer
(129) PM-300: binder polymer which was synthesized in the above description
(130) (b) Photopolymerizable compound
(131) TMPTA: trimethylolpropane triacrylate (made by Nippon Kayaku Co., Ltd.)
(132) (c) Photopolymerization initiator
(133) OXE-01: 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (made by BASF)
(134) (Other components)
(135) AW-500: Phenol-based polymerization inhibitor (made by Kawaguchi Chemical Industry Co., Ltd.)
(136) SH-30: Silicone leveling agent (made by Dow Corning Toray Co., Ltd.)
Production of Photosensitive Element
Example 1
(137) The solution of the photosensitive resin composition which was obtained in the above description was uniformly applied on a polyethylene terephthalate film (product name Cosmo Shine A-1517 made by TOYOBO CO., LTD.) with a thickness of 16 m. Drying treatment was sequentially conducted in hot air convection type driers of 70 C. and 110 C., and thereby a photosensitive layer was formed of which the thickness after having been dried was 5 m. The photosensitive layer and the protective film (product name E-201F made by Oji F-Tex Co., Ltd.) were laminated on each other, and thereby a photosensitive element was obtained in which the polyethylene terephthalate film (support film), the photosensitive layer and the protective film were laminated in this order. The obtained photosensitive element was wound in a rolled form around a core having a cylindrical shape (outer diameter of 84 mm and inner diameter of 76 mm) so that the support film was arranged at the most outer side, with a tension of 90 N/m.
Examples 2 to 4, and Comparative Examples 1 to 6
(138) The photosensitive element was obtained in a similar way to that in Example 1, except that a protective film shown in Table 3 was used in place of the protective film (product name E-201F made by Oji F-Tex Co., Ltd.).
(139) <Measurement of Surface Roughness>
(140) The arithmetic mean roughness (Ra) and the maximum height (Rmax) of both of the surfaces of the protective film were measured according to the following procedures.
(141) (a) A sample to be measured having a size of 5 cm10 cm was cut out from the protective film.
(142) (b) After one drop of water was dripped on a flat glass substrate (10 cm10 cm) with a dropping pipette, the sample to be measured was brought into pressure contact with the glass substrate so that the air bubble did not enter, with a clean roller.
(143) (c) Both of the ends in the longitudinal direction of the sample to be measured were fixed by weights, and ten portions of measurement regions (region of 284.1 m213.1 m) in the sample to be measured were arbitrarily selected.
(144) (d) After the measurement regions were observed with a 50-times object lens with the use of the shape measuring laser microscope (VK-X200 made by KEYENCE CORPORATION), and also the arithmetic mean roughness (Ra) and the maximum height (Rmax) were measured, the average value of the total 10 portions was calculated.
(145) (e) The above described steps (a) to (d) were repeated to acquire the measurement values three times in total; and the average value of the repeated three times was adopted as the arithmetic mean roughness (Ra) and the maximum height (Rmax).
(146) <Measurement of Average Light Transmittance>
(147) The average light transmittance of the photosensitive element in a wavelength region of the 400 to 700 m was measured with the use of a UV spectrometer (228A type W beam spectrophotometer made by Hitachi, Ltd.)
(148) <Evaluation of Air Bubble (Void) in Laminate>
(149) The protective film was peeled off, and then, as shown in FIG. 1, a photosensitive layer of a photosensitive element (width of 495 mm) of 500 mm was transferred onto a base material (PET film with thickness of 125 m and width of 500 mm, product name A-4300 made by TOYOBO CO., LTD.) on the following lamination conditions. The support film was peeled off, then the surfaces of three predetermined measurement regions (Regions A1, A2 and A3 each with 1 cm1 cm shown in
(150) [Lamination Conditions]
(151) Temperature of laminate rolls: 90 C. (both of upper and lower rolls)
(152) Lamination speed; 2.0 m/minute
(153) Roll linear pressure: 0.63 MPa
(154) The evaluation results of Examples 1 to 4 and Comparative examples 1 to 6 are shown in Table 3. Incidentally, in the columns of the arithmetic mean roughness (Ra) and the maximum height (Rmax), first surface is the surface of the protective film, which comes in contact with the photosensitive layer, and second surface is the surface of the protective film, which does not come in contact with the photosensitive layer.
(155) In addition, one example of the observation results of Example 1 and Comparative example 1 in the evaluation of the air bubble in laminate is shown in
(156) TABLE-US-00003 TABLE 3 Thickness of Thickness of Number of air protective photosensitive Ra (m) Rmax (m) Average bubbles in Protective film element (First surface/ (First surface/ transmittance laminate Item film (m) (m) second surface) second surface) (%) (pieces/cm.sup.2) Example 1 E-201F 30 51 0.05/0.05 0.5/0.5 89.83 None Example 2 OPP film A 25 46 0.02/0.02 0.26/0.26 89.78 1 Example 3 OPP film B 20 41 0.04/0.04 0.35/0.35 89.64 2 Example 4 OPP film C 15 36 0.03/0.03 0.31/0.31 87.66 2 Comparative NF-15 20 41 0.08/0.08 3.2/3.2 89.35 12 example 1 Comparative E-200C 20 41 0.12/0.11 0.67/0.99 89.73 >100 example 2 Comparative E-201 12 33 0.05/0.09 0.50/0.61 89.75 >100 example 3 Comparative EM-501 15 36 0.10/0.10 1.5/1.0 88.38 >100 example 4 Comparative MA-411 15 36 0.45/0.05 4.0/0.5 87.62 >100 example 5 Comparative MA-420 35 56 0.10/0.10 1.0/1.0 87.93 >100 example 6
(157) The details of the protective film shown in Table 3 are as follows.
(158) E-201F: double-sided smooth polypropylene film (made by Oji F-Tex Co., Ltd.)
(159) OPP film A: polypropylene film (sample product)
(160) OPP film B: polypropylene film (sample product)
(161) OPP Film C: polypropylene film (sample product)
(162) NF-15: double-sided uneven polyethylene film (made by TAMAPOLY CO., LTD.)
(163) E-200C: double-sided uneven polypropylene film (made by Oji Paper Co., Ltd.)
(164) E-201: single-sided smooth polypropylene film (made by Oji F-Tex Co., Ltd.)
(165) EM-501: double-sided finely roughened polypropylene film (made by Oji F-Tex Co., Ltd.)
(166) MA-411: highly-roughened/smooth polypropylene film (made by Oji F-Tex Co., Ltd.)
(167) MA-420: roughened/roughened polypropylene film (made by Oji F-Tex Co., Ltd.)
(168) As is shown in Table 3, the use of the photosensitive element having the protective film of which the both of the surfaces are smooth can suppress the occurrence of the air bubble at the time of the lamination, even when the photosensitive element has the thin photosensitive layer.
Example 5
(169) The thickness of the photosensitive layer of Example 1 was changed to 20 m, and the photosensitive element was obtained in a similar way to that in Example 1. The obtained photosensitive element was wound in a rolled form around a core having a cylindrical shape, then the occurrence of the air bubble in laminate was checked in a similar way to that in Example 1, and as a result, the air bubble was not formed.
INDUSTRIAL APPLICABILITY
(170) According to the present invention, it is possible to suppress the occurrence of the air bubble at the time of lamination, even when the photosensitive element has the thin photosensitive layer. According to the present invention, it is possible to suppress the occurrence of the air bubble at the time of the lamination, even when the photosensitive element has the photosensitive layer of 10 m or less, in particular.
REFERENCE SIGNS LIST
(171) 1, 1a, 1b, 100 . . . photosensitive element, 10, 110 . . . support film, 20, 120 . . . photosensitive layer, 22, 422, 423 . . . protective film, 30, 130 . . . protective film, 30a, 130a . . . principal surface (first surface), 30b, 130b . . . principal surface (second surface), 40 . . . electroconductive layer, 200 . . . base material for touch panel, 210, 220 . . . electrode for touch panel, 230 . . . photomask, 300 . . . base material for touch panel provided with cured film, 400, 500, 600 . . . touch panel, 401, 501, 601 . . . transparent substrate, 402 . . . touch screen, 403, 404, 503, 504, 604 . . . transparent electrode, 405, 505a, 505b, 605 . . . drawing wire, 406 . . . connection electrode, 407 . . . connection terminal, 504a . . . electroconductive material portion, 504b . . . bridge portion, 524, 625 . . . insulating film, 604a . . . transparent electrode wire, 608 . . . opening, A, B . . . unevenness, A1, A2, A3 . . . measurement region, C . . . region, F1 . . . photosensitive layer, F2 . . . PET film, and L . . . active rays.