CN106966074B - Photosensitive resin laminate roll - Google Patents
Photosensitive resin laminate roll Download PDFInfo
- Publication number
- CN106966074B CN106966074B CN201710224203.2A CN201710224203A CN106966074B CN 106966074 B CN106966074 B CN 106966074B CN 201710224203 A CN201710224203 A CN 201710224203A CN 106966074 B CN106966074 B CN 106966074B
- Authority
- CN
- China
- Prior art keywords
- photosensitive resin
- roll
- resin laminate
- annular sheet
- face
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011347 resin Substances 0.000 title claims abstract description 212
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- 238000004804 winding Methods 0.000 claims abstract description 23
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 24
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- 239000000463 material Substances 0.000 claims description 18
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
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- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B65D59/00—Plugs, sleeves, caps, or like rigid or semi-rigid elements for protecting parts of articles or for bundling articles, e.g. protectors for screw-threads, end caps for tubes or for bundling rod-shaped articles
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- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
- B65D81/30—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants by excluding light or other outside radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/67—Containers, packaging elements or packages, specially adapted for particular articles or materials for web or tape-like material
- B65D85/671—Containers, packaging elements or packages, specially adapted for particular articles or materials for web or tape-like material wound in flat spiral form
- B65D85/672—Containers, packaging elements or packages, specially adapted for particular articles or materials for web or tape-like material wound in flat spiral form on cores
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H75/00—Storing webs, tapes, or filamentary material, e.g. on reels
- B65H75/02—Cores, formers, supports, or holders for coiled, wound, or folded material, e.g. reels, spindles, bobbins, cop tubes, cans, mandrels or chucks
- B65H75/18—Constructional details
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H75/00—Storing webs, tapes, or filamentary material, e.g. on reels
- B65H75/02—Cores, formers, supports, or holders for coiled, wound, or folded material, e.g. reels, spindles, bobbins, cop tubes, cans, mandrels or chucks
- B65H75/18—Constructional details
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0012—Processes making use of the tackiness of the photolithographic materials, e.g. for mounting; Packaging for photolithographic material; Packages obtained by processing photolithographic materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Food Science & Technology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Packaging Of Machine Parts And Wound Products (AREA)
- Storage Of Web-Like Or Filamentary Materials (AREA)
- Packages (AREA)
Abstract
The invention provides a photosensitive resin laminate roll which can easily remove foreign matters from the end face of the photosensitive resin laminate roll during unsealing. The photosensitive resin laminate roll is configured by winding a photosensitive resin laminate in a roll shape around a core and disposing a roll end face protection member in contact with an end face of the wound photosensitive resin laminate, wherein the roll end face protection member has an adhesive composition on a side in contact with the roll end face, and the photosensitive resin laminate comprises at least a support layer and a photosensitive resin layer laminated on the support layer.
Description
The present application is a divisional application of an application entitled "photosensitive resin laminate roll" having an application date of 2013, 12 and 26 months, and an application number of 2013800685642.
Technical Field
The present invention relates to a photosensitive resin laminate roll.
Background
Conventionally, several methods have been disclosed as a package of a photosensitive element. For example, a package in which an end face protection member is provided to protect the end face of a roll is disclosed (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2005-41537
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a photosensitive resin laminate roll in which foreign matter can be easily removed from the end face of the photosensitive resin laminate roll when unsealing.
Means for solving the problems
The above problems can be solved by the following means of the present invention. Namely, the invention is as follows:
[1]
a photosensitive resin laminate roll in which a photosensitive resin laminate is wound in a roll shape around a winding core, a roll end face protection member is disposed so as to be in contact with an end face of the wound photosensitive resin laminate,
the roll end face protecting member has an adhesive composition on the side for contact with the roll end face,
the photosensitive resin laminate comprises at least a support layer and a photosensitive resin layer laminated on the support layer.
[2]
The roll of photosensitive resin laminate according to item [1], which is covered with a light-shielding sheet.
[3]
The roll of photosensitive resin laminate according to [2], wherein the light-shielding sheet has a cylindrical shape.
[4]
The roll of a photosensitive resin laminate according to any one of [1] to [3], wherein,
the length of the core is longer than the width of the photosensitive resin laminate,
the roll end face protection member is an annular sheet disposed on an end face of the photosensitive resin laminate wound in a roll shape, and the annular sheet is disposed so as to penetrate through an extension portion of the winding core.
[5]
The roll of the photosensitive resin laminate according to item [4], wherein the inner diameter of the annular sheet is 1 to 1.1 times the outer diameter of the core.
[6]
The roll of photosensitive resin laminate according to item [4] or [5],
the annular sheet is disposed on a horizontally extending flat plate so that a half of the annular sheet is present in the air, and H/R is 0.06-0.59 when the distance between the distal end of the annular sheet farthest from the flat plate in the portion of the annular sheet present in the air and the surface of the flat plate on the side contacting the annular sheet is defined as a bending distance H (mm) and the half of the outer diameter of the annular sheet is defined as R (mm).
[7]
The roll of a photosensitive resin laminate according to any one of [1] to [6], wherein the end-face protection member has an adhesion force to the low-density polyethylene film of 5gf/inch to 250 gf/inch.
[8]
The roll of the photosensitive resin laminate according to any one of [1] to [7], wherein the substrate of the roll end surface protection member is a non-dust paper, a low-dust paper, a synthetic paper, or a paper obtained by laminating a resin substrate with a paper.
[9]
The photosensitive resin laminate roll according to any one of [1] to [8], wherein the photosensitive resin layer is a layer containing a photosensitive resin composition containing an alkali-soluble polymer having a carboxyl group, an addition-polymerizable monomer, and a photopolymerization initiator.
[10]
The photosensitive resin laminate roll according to [9], wherein the alkali-soluble polymer having a carboxyl group is a copolymer of styrene or a derivative thereof.
[11]
The photosensitive resin laminate roll according to item [9] or [10], wherein the addition polymerizable monomer comprises a bisphenol A (meth) acrylate compound.
[12]
The photosensitive resin laminate roll according to any one of [9] to [11], wherein the photopolymerization initiator contains hexaarylbiimidazole or a derivative thereof.
[13]
The photosensitive resin laminate roll according to any one of [1] to [12], wherein the adhesive composition contains an acrylic resin.
[14]
The photosensitive resin laminate roll according to any one of [1] to [13], wherein the binder composition contains a binder and particles, 50% by mass or more of the particles have a diameter of 80 to 120% of a coating thickness of the binder composition, and the content of the particles is 5 to 30 parts by weight with respect to 100 parts by weight of the binder.
[15]
A method for manufacturing a photosensitive resin laminate roll, characterized in that,
a photosensitive resin laminate wound in a roll shape around a winding core, and a roll end face protection member disposed so as to contact an end face of the wound photosensitive resin laminate,
the length of the core is longer than the width of the photosensitive resin laminate,
the photosensitive resin laminate comprises at least a support layer and a photosensitive resin layer laminated on the support layer,
the roll end face protection member has an adhesive composition on the side in contact with the roll end face,
the roll end face protection member is an annular sheet material comprising: the annular sheet is integrally or partially disposed on an end face of the rolled photosensitive resin laminate, and the inner diameter of the annular sheet after the annular sheet is disposed on the end face of the rolled photosensitive resin laminate is 1 to 1.1 times the outer diameter of the core.
[16]
The method of manufacturing a photosensitive resin laminate roll according to item [15], wherein the inner diameter of the annular sheet is 1.001 to 1.1 times the outer diameter of the core, and the annular sheet is disposed so as to penetrate through a protruding portion of the core.
[17]
The method for producing a photosensitive resin laminate roll according to item [15] or [16], wherein the photosensitive resin laminate roll is a laminate roll,
the annular sheet is disposed on a horizontally extending flat plate so that a half of the annular sheet is present in the air, and H/R is 0.06-0.59 when the distance between the distal end of the annular sheet farthest from the flat plate in the portion of the annular sheet present in the air and the surface of the flat plate on the side contacting the annular sheet is defined as a bending distance H (mm) and the half of the outer diameter of the annular sheet is defined as R (mm).
[18]
The method for producing a roll of a photosensitive resin laminate according to any one of [15] to [17], wherein the adhesive strength between the annular sheet and the low-density polyethylene film is 5gf/inch to 250 gf/inch.
[19]
A method for packaging a photosensitive resin laminate roll, characterized in that a photosensitive resin laminate roll is manufactured by the method according to any one of claims 15 to 18, and the photosensitive resin laminate roll is further covered with a cylindrical light-shielding sheet.
[20]
An annular sheet for a film roll in which a film is wound around a winding core, wherein,
the length of the roll core is longer than the width of the film,
the inner diameter of the annular sheet is 1-1.1 times of the outer diameter of the winding core, and
the annular sheet is in contact with an end face of the wound film, has an adhesive composition on the side of the annular sheet in contact with the end face, and is disposed on the film roll so as to penetrate through the extension portion of the core.
[21]
The annular sheet according to [20], wherein the film is a photosensitive resin laminate.
[22]
The endless sheet according to item [20] or [21], characterized in that,
the annular sheet is disposed on a horizontally extending flat plate so that a half of the annular sheet is present in the air, and H/R is 0.06-0.59 when the distance between the distal end of the annular sheet farthest from the flat plate in the portion of the annular sheet present in the air and the surface of the flat plate on the side contacting the annular sheet is defined as a bending distance H (mm) and the half of the outer diameter of the annular sheet is defined as R (mm).
[23]
The annular sheet according to any one of [20] to [22], wherein the adhesive strength with respect to the low-density polyethylene film is 5gf/inch to 250 gf/inch.
[24]
The loop sheet according to any one of [20] to [23], wherein the base material is a non-dust paper, a low-dust paper, a synthetic paper, or a paper laminated with a resin base material.
[25]
The annular sheet according to any one of [21] to [24], wherein the photosensitive resin layer is a layer containing a photosensitive resin composition containing an alkali-soluble polymer having a carboxyl group, an addition-polymerizable monomer, and a photopolymerization initiator.
[26]
The annular sheet according to [25], wherein the alkali-soluble polymer having a carboxyl group is a copolymer of styrene or a derivative thereof.
[27]
The cyclic sheet according to item [25] or [26], wherein the addition polymerizable monomer comprises a bisphenol A-based (meth) acrylate compound.
[28]
The cyclic sheet according to any one of [25] to [27], wherein the photopolymerization initiator contains hexaarylbiimidazole or a derivative thereof.
[29]
The annular sheet according to any one of [20] to [28], wherein the adhesive composition contains an acrylic resin.
[30]
The endless sheet according to any one of [20] to [29], wherein the binder composition contains a binder and particles, 50% by mass or more of the particles have a diameter of 80 to 120% of a coating thickness of the binder composition, and the content of the particles is 5 to 30 parts by weight with respect to 100 parts by weight of the binder.
[31]
A film roll comprising the annular sheet described in [20] to [30] covered with a light-shielding sheet.
ADVANTAGEOUS EFFECTS OF INVENTION
When the photosensitive resin laminate roll of the present invention is used, foreign matter can be easily removed from the end face of the photosensitive resin laminate roll at the time of unsealing.
Drawings
Fig. 1 is a schematic view of an embodiment of a photosensitive resin laminate roll in which a photosensitive resin laminate is wound in a roll shape around a core and a roll end surface protection member is disposed so as to contact an end surface of the wound photosensitive resin laminate.
Fig. 2 is a diagram showing the bending distance H and the half R of the outer diameter of the annular sheet.
Fig. 3 is a schematic view showing an embodiment of a photosensitive resin laminate roll covered with a cylindrical light-shielding sheet.
Detailed Description
The best mode for carrying out the present invention (hereinafter, simply referred to as "embodiment") will be described in detail below. The present invention is not limited to the following embodiments, and can be implemented by being variously modified within the scope of the gist thereof.
The photosensitive resin laminate roll is a photosensitive resin laminate roll in which a long (strip-shaped) photosensitive resin laminate is wound around a core in the longitudinal direction thereof, and a roll end surface protection member is disposed so as to be in contact with the end surface of the wound photosensitive resin laminate (the end portion side in the width direction of the strip-shaped photosensitive resin laminate).
Fig. 1 is a schematic view of an embodiment of such a photosensitive resin laminate roll 10. Here, the photosensitive resin laminate 1 includes a support layer 4, a photosensitive resin layer 5 laminated on the support layer, and an optional protective layer 6, and the laminate 1 is wound around a core 2. Further, end-face-winding protection members 3 are provided in contact with both end faces of the wound photosensitive resin laminate. Here, the roll end face protection member 3 is shown as an annular sheet.
(photosensitive resin laminate)
The photosensitive resin laminate includes at least a support layer and a photosensitive resin layer laminated on the support layer, and preferably further includes a protective layer laminated on the photosensitive resin layer. The photosensitive resin laminate further includes a photosensitive film called a dry film resist or a dry film photoresist.
The support layer may be of any structure as long as it supports the photosensitive resin layer. As the support layer that can be used, a transparent layer that transmits light emitted from an exposure light source is preferable. Examples of such a support layer include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may be used after being stretched as required. From the viewpoint of resolution, a film having a haze of 5 or less is preferable. The haze is more preferably 3 or less, still more preferably 2.5 or less, and still more preferably 1 or less. The thickness of the support layer is preferably 10 μm to 30 μm, although a thin layer is advantageous in terms of image formability and economy, since it is necessary to maintain thermal shrinkage when the photosensitive resin composition layer is applied. Examples thereof include GR19, GR16 manufactured by DuPont film (strain), R310-16 manufactured by Mitsubishi Plastics, Inc., R340G16 manufactured by Mitsubishi Plastics, FB40(16 μm film thickness) manufactured by Bao レポリエステルフィルム (strain), FB60(16 μm film thickness), and the like.
The protective layer is sufficiently smaller in adhesion force with the photosensitive resin layer than the support layer, and therefore can be easily peeled off. For example, as the protective layer, a polyethylene film, a polypropylene film, a stretched polypropylene film, or the like can be preferably used. Further, a film excellent in releasability disclosed in Japanese patent application laid-open No. 59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm. Examples thereof include GF-18, GF-818 and GF-858 manufactured by Tamapoly Co., Ltd.
The photosensitive resin layer can be laminated by applying a photosensitive resin composition to a support layer and drying the applied composition. The thickness of the photosensitive resin layer is preferably 5 to 100 μm, and the upper limit is more preferably 50 μm. The thickness of the photosensitive resin layer is appropriately selected according to the application because the resolution is improved as the thickness approaches 5 μm, and the film strength is improved as the thickness approaches 100 μm.
As a method for producing the photosensitive resin laminate, a conventionally known method can be employed. For example, a photosensitive resin composition used for a photosensitive resin layer is mixed with a solvent as a photosensitive resin composition mixed solution, and the mixture is applied to a support layer using a bar coater or a roll coater and dried, and a photosensitive resin layer containing the photosensitive resin composition is laminated on the support layer. The photosensitive resin composition mixture liquid is preferably mixed with a solvent to a temperature of 500 to 4000 mPa.s at 25 ℃. From the viewpoint of the viscosity, drying property, residual solvent amount, coating property and foaming property of the photosensitive resin composition preparation solution, methyl ethyl ketone, acetone, ethanol, methanol, propanol, propylene glycol monomethyl ether acetate, toluene and the like can be used as appropriate as the solvent. Next, a protective layer is laminated on the photosensitive resin layer, whereby a photosensitive resin laminate can be produced.
The photosensitive resin laminate is used in a roll form by being wound around a core in a long shape. The winding length is not particularly limited, and is preferably 320m or less from the viewpoint of the weight of the roll and the ease of handling. The more substrates can be rolled up from the 1 photosensitive resin laminate, the higher the efficiency, and therefore, from the viewpoint of productivity, the winding length is preferably 100m or more.
(roll core)
Winding cores are sometimes also referred to as cores. The shape is not particularly limited, and may be cylindrical or columnar. Since the photosensitive resin laminate is used for an electronic material as an etching or plating resist and a permanent pattern, a winding core subjected to dust-free treatment is preferable, and a winding core made of a plastic resin is preferable. The plastic resin is preferably light, high in strength, and dust-free. Polypropylene (PP) resin, acrylonitrile-butadiene-styrene (ABS) resin, nylon resin, polyvinyl chloride resin, etc. can be used, with ABS resin being preferred. The diameter of the core is not particularly limited, and when the photosensitive resin laminate is wound and mounted in a laminating apparatus, the core preferably has a diameter of 2 to 5 inches, more preferably 3 inches, so as to be mounted in the apparatus. The length of the core (axial length when a cylindrical or columnar core is used) may be the same as or shorter than the width of the photosensitive resin laminate, but when the photosensitive resin laminate is wound, the length of the core is preferably longer than the width of the photosensitive resin laminate so that appropriate protruding portions can be secured on both sides. It is preferable that the annular sheet is attached so as to penetrate the protruding portion. Further, a bearing called a core holder may be fitted to the protruding portion to store the photosensitive resin laminate roll in a suspended state so that the photosensitive resin laminate roll does not move.
(roll end face protection member)
The roll end face protection member is disposed so as to be in contact with the end face of the wound photosensitive resin laminate. The shape is not particularly limited, and is not particularly limited as long as the end face is in contact with a certain area and at least a part of the roll end face is covered and protected, and among these, an annular sheet is preferably disposed so as to penetrate the protruding portion of the core so as to be in contact with the end face of the wound photosensitive resin laminate. More preferably, the photosensitive resin laminate roll end surface is formed into a ring shape having a width that can substantially cover the entire photosensitive resin laminate roll end surface. The roll end face protection member may be used only at one end of the wound photosensitive resin laminate, but is preferably used at both ends.
When the roll end surface protecting member is an annular sheet, the inner diameter of the ring is preferably slightly larger than the outer diameter of the core so that the ring can penetrate the core. Further, by slightly offsetting the center of the annular sheet from the center of the core, the outer periphery of the annular sheet is slightly exposed from the outer periphery of the photosensitive resin laminate wound in a roll shape. In this way, the ring inner diameter is preferably slightly larger than the outer diameter of the core, since the removal of the ring-shaped sheet material becomes easy. Specifically, it is preferable that the inner diameter of the ring is 1.001 times or more the outer diameter of the core because no blockage occurs in the core (Japanese: り and き). More preferably 1.005 times or more, and still more preferably 1.01 times or more. From the viewpoint of protecting the entire roll end face and removing foreign matter, the ring inner diameter is preferably 1.1 times or less, more preferably 1.05 times or less, and still more preferably 1.03 times or less the outer diameter of the roll core.
The outer diameter of the ring is preferably 0.99 times or more, more preferably 1 time or more, the outer diameter of the photosensitive resin laminate wound in a roll so that the end face of the photosensitive resin laminate roll can be covered. In addition, from the viewpoint of suppressing adhesion to a packaging material such as a cylindrical tube having light-shielding properties covering the photosensitive resin laminate roll, the ring outer diameter is preferably 1.1 times or less, more preferably 1.05 times or less, and even more preferably 1.03 times or less the outer diameter of the photosensitive resin laminate roll.
Examples of the base material of the roll end face protective member include polyester, polyethylene terephthalate, polyphenylene sulfide, polypropylene, nylon, unstretched, stretched, or biaxially stretched materials, and plastic resins such as low-density polyethylene, high-density polyethylene, hard polyvinyl chloride, soft polyvinyl chloride, cellophane, acetate, cellulose triacetate, polystyrene, polycarbonate, and polyimide, dust-treated paper, dust-treated high-quality paper, cleaning paper, and a product in which paper is laminated with the plastic resin, and synthetic paper. Since the photosensitive resin laminate is used for an electronic material as a resist layer, a plating resist layer, and a permanent pattern, a material subjected to dust-free treatment is preferable. The base material is preferably dust-treated paper, dust-treated high-quality paper, clean paper, a product obtained by laminating paper with the plastic resin, or synthetic paper, from the viewpoints of less generation of static electricity, good conformability to the end face, excellent foreign matter removal performance, and excellent mountability. The synthetic paper preferably uses polypropylene as a main raw material.
When the base material is a dust-treated paper, a dust-treated high-quality paper, a clean paper, or a paper laminated with the plastic resin, the thickness of the base material is preferably 50 to 500 μm. From the viewpoint of mountability, it is preferably 50 μm or more, and from the viewpoint of conformability to the end surface and foreign matter removal property, it is preferably 500 μm or less, more preferably 60 to 200 μm, and still more preferably 60 to 150 μm.
The roll end face protection member may have an embossed surface from the viewpoint of mold release properties and stain resistance. The roll end face protection member has an adhesive composition on the side in contact with the end face of the roll of the photosensitive resin laminate. The roll end surface protecting member is preferably an annular sheet member having a circular shape in plan view.
In the above-described annular sheet, the annular sheet is disposed on a horizontally extending flat plate so that a half of the annular sheet is present in the air, and when a distance between a distal end of the annular sheet farthest from the flat plate in a portion of the annular sheet present in the air and a surface of the flat plate on a side contacting the annular sheet is represented by a bending distance H (mm), and a half of an outer diameter of the annular sheet is represented by R (mm), H/R is preferably 0.06 to 0.59. From the viewpoint of the roll end surface mountability of the annular sheet, H/R is preferably 0.59 or less. More preferably 0.5 or less, and still more preferably 0.45 or less. From the viewpoint of the following ability to the roll end face and the foreign matter removal ability, it is preferably 0.06 or more. More preferably 0.1 or more, and still more preferably 0.15 or more.
The bending distance H was measured as follows. First, as shown in fig. 2, the loop sheet 3 is provided on a substantially flat plate 7 extending in a substantially horizontal direction (a direction orthogonal to the vertical direction). At this time, the surface provided with the adhesive was set to face upward so as not to be bonded to the flat plate 7. The ring-shaped sheet 3 is fixed so that a half of the ring-shaped sheet 3 is present in the air, that is, so that the center of the ring-shaped sheet 3 is located at a substantially linear edge present at an end of the flat plate. In the fixing, as shown in fig. 2, the fixing may be performed by using the fixing member 8. At this time, the annular sheet 3 is not bent or folded by influence other than gravity. The vertical distance between the top end of the annular sheet, which is farthest from the edge of the flat plate, and an imaginary plane formed by the surface of the flat plate, which is in contact with the annular sheet, at a portion (portion exposed from the end) present in the air of the annular sheet is measured by an L-shaped scale. The measurement site was Fuji city, Jinggang prefecture, Japan.
(adhesive composition)
As the adhesive composition, a known adhesive composition can be selected and used, which does not cause adhesive residue on the end face of the photosensitive resin film when the roll end face protection member is peeled off, and which does not cause adhesion of the photosensitive resin to the roll end face protection member when the roll end face protection member is peeled off.
Among them, a composition containing an acrylic resin is preferable from the viewpoint of foreign matter removal property and mold release property. The photosensitive resin composition is a photosensitive resin composition containing an alkali-soluble polymer having a carboxyl group, an addition polymerizable monomer, and a photopolymerization initiator, and when the binder composition contains an acrylic resin, the photosensitive resin composition is preferable from the viewpoint of further having both foreign matter removal property and mold release property at a high level.
The binder composition preferably contains particles, 50% by mass or more of which preferably have a diameter of 80 to 120% of the coating thickness of the binder composition, and the content of the particles is 5 to 30 parts by weight with respect to 100 parts by weight of the binder. The diameter of the particles was observed using a microscope, and the maximum diameter was observed for any 100 particles, and the average value thereof was calculated.
The diameter of the particles is preferably 80% or more from the viewpoint of mold releasability, and preferably 120% or less from the viewpoint of tackiness. More preferably 90 to 110%, and still more preferably 100%.
In general, particles of a single particle size are theoretically possible, but in many cases, particles are difficult to obtain. Particles having a particle size distribution which is as narrow as possible, i.e. a sharp particle size curve, are preferred.
Preferably, 50 mass% or more of the total amount of the binder has a diameter of 80 to 120% of the coating thickness of the binder. From the viewpoint of balance between releasability and tackiness, it is more preferably 70% by mass or more, and still more preferably 80% by mass or more.
The content of the particles is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the binder. In the case of the patch, it is preferably 5 parts by weight or more from the viewpoint of air-out-bubbling property, and preferably 30 parts by weight or less from the viewpoint of adhesiveness. More preferably 10 to 25 parts by weight. When the material of the particles is glass, 15 to 30 parts by weight is preferable, and in the case of plastic, 5 to 25 parts by weight is preferable.
The material of the particles is preferably plastic or inorganic material. Examples of the plastic include polymethacrylate, polymethylmethacrylate, polystyrene acrylate, polyethylene, polypropylene, polystyrene butadiene, polystyrene divinylbenzene, polyurethane, polybenzothromazine, and melamine. Examples of the inorganic material include glass, silica (silicate mineral), and calcium carbonate.
The adhesive strength of the adhesive can be improved by lowering the softening temperature of the entire composition and increasing the polarity of the resin component.
The adhesion between the end face protection member and the low density polyethylene film is preferably 5gf/inch to 250gf/inch, more preferably 50gf/inch to 240gf/inch, from the viewpoint of foreign matter removability and mountability.
The adhesion was measured in the following manner. That is, a low-density polyethylene (LDPE) film sheet was attached to the surface of the end-face protection member on which the layer of the adhesive composition was formed by a hand pressure roller. The low density polyethylene film used was GF-858 manufactured by tampooly co. Cut into a rectangular strip with the width of 1inch and the length of 15cm, and the humidity is adjusted for 11 hours at the relative humidity of 50 percent and the temperature of 23 ℃. Tensile tests were carried out using a tensile tester RTM-500 manufactured by Orientec Co., Ltd at a tensile speed of 100 mm/min under a load cell of 1 kg. At this time, the end face protection member of the sample was held (fixed) by the lower portion of the Tensilon, and the low density polyethylene film was held (fixed) by the stretching portion, and a tensile test was performed. In the tensile test, the integral average of the load was taken in the interval of 10mm to 50mm in tension, and the number of tests was taken as an average of 2 times, and this was taken as the value of the adhesiveness.
(method for producing photosensitive resin laminate roll)
The photosensitive resin laminate roll is preferably covered with a light-shielding sheet from the viewpoint of suppressing adhesion of foreign matter and suppressing light sensitivity during transportation. The light-shielding sheet may also be referred to as a light-shielding film. The light-shielding sheet may cover the photosensitive resin laminate roll so as to be wound around the photosensitive resin laminate roll. As shown in fig. 3, when the light-shielding sheet 9 is cylindrical, the photosensitive resin roll 1 can be inserted into the cylinder to cover the photosensitive resin roll 1, which is preferable. Further, if the length of the tube is longer than the core 2 of the photosensitive resin laminate roll 1, as shown in fig. 3, the portion longer than the core 2 is preferably folded into the core to further suppress adhesion of foreign matter and light reception.
The light-shielding sheet is preferably made of polyethylene from the viewpoint of protecting the photosensitive resin laminate roll from contact with, for example, light falling objects or light contact of the packaging container. The film thickness is preferably 10 μm or more from the viewpoint of maintaining suitable strength and suppressing pin holes, and is preferably 300 μm or less from the viewpoint of handling property. More preferably 20 to 200 μm, and still more preferably 30 to 130 μm. Black is preferable for improving light-shielding properties.
The photosensitive resin laminate roll is preferably suspended and fixed by a pair of members called core holders each having a projection to be fitted to the core. The photosensitive resin laminate can be prevented from contacting the floor wall surface of the packaging container during transportation by being suspended and fixed. Examples of the core holder include core holders described in japanese patent application laid-open nos. 2004 and 42952 and 2003 and 89477.
When the photosensitive resin laminate roll is covered with the light-shielding sheet, it is preferable to fold a portion of the light-shielding sheet longer than the core into the core and further mount the core holder so as to sandwich the folded portion, because adhesion of foreign matter and sensitization can be suppressed.
(photosensitive resin composition)
The photosensitive resin composition preferably contains (a) an alkali-soluble polymer containing a carboxyl group; (b) an addition polymerizable monomer; (c) a photopolymerization initiator.
From the viewpoint of reducing the amount of residual glue on the roll end surface when peeling the annular sheet from the roll end surface and reducing the adhesion of the photosensitive resin composition to the annular sheet, it is preferable that the photosensitive resin composition contains the above-mentioned components (a) to (c).
(a) Alkali-soluble polymer having carboxyl group
(a) The carboxyl group-containing alkali-soluble polymer preferably contains α -unsaturated carboxyl group-containing monomer as a polymerization component, has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, and is essential for imparting developability or releasability to a developer or a release solution containing an aqueous alkali solution to the photosensitive resin composition, the acid equivalent is the mass of the alkali-soluble polymer having 1 equivalent of carboxyl group therein, the acid equivalent has a more preferable lower limit of 250 and a more preferable upper limit of 450, the acid equivalent is preferably 100 or more from the viewpoints of improvement in development resistance and improvement in resolution and adhesion, and from the viewpoints of ensuring compatibility with other components in a solvent or a photosensitive resin composition, particularly with an addition polymerizable monomer described below (b), and the acid equivalent is preferably 600 or less from the viewpoints of improvement in developability and releasability, and the measurement of the acid equivalent is carried out by titration using a sodium hydroxide titration method using 0.1mol/L sodium hydroxide (COM-555) manufactured by Heiping Hei.
(a) The weight average molecular weight of the alkali-soluble polymer containing a carboxyl group is preferably 5,000 to 500,000. The weight average molecular weight is preferably 5,000 or more from the viewpoint of maintaining the thickness of the photosensitive resin laminate uniform and obtaining resistance to a developer, and from the viewpoint of suppressing the edge melting, and is preferably 500,000 or less from the viewpoint of maintaining the developability. The bead refers to a phenomenon in which the photosensitive resin composition bleeds out from the roll end face when the photosensitive resin laminate is wound in a roll. The exuded photosensitive resin composition may be stuck to the photosensitive resin composition exuded from the photosensitive resin layer of another adjacent layer via the support layer protective layer in a rolled state. The photosensitive resin composition after blocking, that is, the photosensitive resin composition after edge melting, may separate from the photosensitive resin laminate in a roll form, peel off from the end face at the time of lamination, and scatter as resist dust. When the resist dust adheres to the laminated substrate, the resist dust adheres to a mask for subsequent exposure, is exposed and cured, and in the case of a negative resist, the exposure is blocked, resulting in a defective pattern.
More preferably, the lower limit of the weight average molecular weight of the (a) carboxyl group-containing alkali-soluble polymer is 20,000, and the upper limit of the weight average molecular weight of the (a) carboxyl group-containing alkali-soluble polymer is 250,000. The weight average molecular weight in the present specification means a weight average molecular weight measured by Gel Permeation Chromatography (GPC) using a standard curve of polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.).
(a) The weight average molecular weight of the alkali-soluble polymer containing a carboxyl group can be measured using a gel permeation chromatography manufactured by JASCO Corporation under the following conditions:
refractive index detector: RI-1530
A pump: PU-1580
A degassing device: DG-980-50
Column oven: CO-1560
Column: KF-8025, KF-806 MX 2 and KF-807
Eluent: THF.
(a) The alkali-soluble polymer having a carboxyl group is preferably a (co) polymer containing 1 or more monomers selected from the first monomer and the second monomer described later as components.
The first monomer is a carboxylic acid or an acid anhydride having one polymerizable unsaturated group in the molecule. Examples thereof include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride and maleic acid half-esters. Among them, (meth) acrylic acid is particularly preferable.
The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples thereof include esters of vinyl alcohol such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, and vinyl acetate; (meth) acrylonitrile, styrene, and a styrene derivative capable of polymerization, and the like. Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene and benzyl (meth) acrylate are preferable, and styrene is particularly preferably used from the viewpoint of resolution.
(a) The alkali-soluble polymer having a carboxyl group is preferably synthesized by mixing the above monomers and diluting the mixture with a solvent such as acetone, methyl ethyl ketone or isopropyl alcohol, adding a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile in an appropriate amount, and heating and stirring the mixture. Sometimes, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be added to adjust the concentration to a desired level. As the synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
Particularly preferred (a) the carboxyl group-containing alkali-soluble polymer is one in which the copolymerization ratio of the first monomer to the second monomer is 10 to 60% by mass of the first monomer and 40 to 90% by mass of the second monomer, and more preferably 15 to 35% by mass of the first monomer and 65 to 85% by mass of the second monomer.
More specific examples of the carboxyl group-containing alkali-soluble polymer (a) include polymers containing methyl methacrylate, methacrylic acid and styrene as copolymerization components, polymers containing methyl methacrylate, methacrylic acid and n-butyl acrylate as copolymerization components, and polymers containing benzyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate as copolymerization components.
The content of the carboxyl group-containing alkali-soluble polymer (a) in the photosensitive resin composition is in the range of 20 to 90% by mass, preferably 40 to 60% by mass, based on the total solid content of the photosensitive resin composition. (a) The content of the carboxyl group-containing alkali-soluble polymer is preferably 20 mass% or more from the viewpoint of maintaining the alkali developability of the photosensitive resin composition and the characteristics of a resist pattern formed by exposure and development as a resist layer, for example, sufficient resistance in the indentation, etching, and various plating steps, and is preferably 90 mass% or less from the viewpoint of sufficient flexibility of the photosensitive resin composition before curing and the resist pattern after curing.
(b) Addition polymerizable monomer
(b) The addition polymerizable monomer is a compound having at least one polymerizable ethylenically unsaturated bond in the molecule. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group. Further, from the viewpoint of high resolution, meltability, and indentation property, it is preferable to use at least one bisphenol a (meth) acrylate compound as the addition polymerizable monomer (b).
In the present specification, the bisphenol A-based (meth) acrylate compound means-C derived from bisphenol A6H4-C(CH3)2-C6H4A group and a compound having a (meth) acryloyl group or a carbon-carbon unsaturated double bond derived from a (meth) acryloyl group. Specific examples thereof include di (meth) acrylate of polyethylene glycol having an average of 2 units of ethylene oxide added to both ends of bisphenol A (NK ester BPE-200 manufactured by Ninghamu chemical industry Co., Ltd.), dimethacrylate of polyethylene glycol having an average of 5 units of ethylene oxide added to both ends of bisphenol A (NK ester BPE-500 manufactured by Ninghamu chemical industry Co., Ltd.), di (meth) acrylate of polyalkylene glycol having an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide added to both ends of bisphenol A, and di (meth) acrylate of polyalkylene glycol having an average of 15 units of ethylene oxide and an average of 2 units of propylene oxide added to both ends of bisphenol A.
As the addition polymerizable monomer (b), in addition to the above-mentioned compounds, known compounds having at least one ethylenically unsaturated group can be used. Examples thereof include 4-nonylphenylheptaethyleneglycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexyleneglycol acrylate, reaction products of a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate with propylene oxide (trade name OE-A200, manufactured by Nippon catalyst Chemicals), polyoxyalkylene glycol di (meth) acrylates such as 4-n-octylphenoxypentapropyleneglycol acrylate, 1, 6-hexanediol (meth) acrylate, 1, 4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, and mixtures thereof, And polyfunctional (meth) acrylates containing a urethane group such as trimethylolpropane triglycidyl ether tri (meth) acrylate, 2-bis (4-methacryloxypentaethoxyphenyl) propane, and urethane compounds of hexamethylene diisocyanate and nonyleneglycol monomethacrylate, and polyfunctional (meth) acrylates of isocyanurate compounds. These may be used alone, two or more of them may be used in combination, or they may be used in combination with a bisphenol a (meth) acrylate compound.
The content of the addition polymerizable monomer (b) in the photosensitive resin composition is in the range of 5 to 75% by mass, more preferably 15 to 70% by mass, based on the total solid content of the photosensitive resin composition. The content of the (b) addition polymerizable monomer is 5 mass% or more from the viewpoint of resolution, adhesiveness, and copper wire formability, and 75 mass% or less from the viewpoint of flexibility of the cured film.
(c) Photopolymerization initiator
As the photopolymerization initiator (c), for example, those generally used as photopolymerization initiators for photosensitive resins can be suitably used, and hexaarylbiimidazole (hereinafter also referred to as triarylimidazole dimer) is particularly preferably used.
Examples of triarylimidazole dimers include: 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer (hereinafter also referred to as "2, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 1 ' -biimidazole"), 2 ', 5-tris- (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenylimidazole dimer, 2, 4-bis- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylimidazole dimer,
2,4, 5-tris- (o-chlorophenyl) -diphenylimidazole dimer, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) -imidazole dimer, 2 ' -bis- (2-fluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazole dimer, 2 ' -bis- (2, 3-difluoromethylphenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazole dimer, 2 ' -bis- (2, 4-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazole dimer,
2,2 '-bis- (2, 5-difluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -imidazole dimer, 2' -bis- (2, 6-difluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazole dimer, 2 '-bis- (2,3, 4-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -imidazole dimer, 2' -bis- (2,3, 5-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -imidazole dimer,
2,2 ' -bis- (2,3, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazole dimer, 2 ' -bis- (2,4, 5-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazole dimer, 2 ' -bis- (2,4, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazole dimer,
2,2 ' -bis- (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazole dimer, 2 ' -bis- (2,3,4, 6-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazole dimer, and 2,2 ' -bis- (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -imidazole dimer, and the like.
In particular, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, which is a photopolymerization initiator having a high effect on resolution or strength of a cured resist film, can be preferably used. These photopolymerization initiators may be used alone, or two or more kinds may be used in combination. In addition, the following acridine compound, pyrazoline compound, and the like can be used in combination.
In a preferred embodiment, an acridine compound or a pyrazoline compound can be used as the (c) photopolymerization initiator. The acridine compound includes acridine, 9-phenylacridine, 9- (4-tolyl) -acridine, 9- (4-methoxyphenyl) acridine, 9- (4-hydroxyphenyl) acridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine,
9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-tert-butylphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine,
9- (4-bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine. Among them, 9-phenylacridine is preferable.
As the pyrazoline compound, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferable.
Examples of the photopolymerization initiator other than the above-mentioned photopolymerization initiators include quinones such as 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone and 3-chloro-2-methylanthraquinone,
aromatic ketones such as benzophenone, Michler's ketone [4,4 ' -bis (dimethylamino) benzophenone ] and 4,4 ' -bis (diethylamino) benzophenone, benzoin ethers such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin and ethylbenzoin,
oxime esters such as benzildimethylketal, benzildiethylketal, a combination of thioxanthone and alkylaminobenzoic acid, 1-phenyl-1, 2-propanedione-2-O-benzoinoxime, and 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime.
Examples of the above-mentioned combination of a thioxanthone and an alkylaminobenzoic acid include a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and a combination of isopropylthioxanthone and ethyl dimethylaminobenzoate. In addition, N-aryl amino acids may also be used. Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among them, N-phenylglycine is particularly preferable.
The content of the photopolymerization initiator (c) in the photosensitive resin composition is in the range of 0.01 to 30% by mass based on the total solid content of the photosensitive resin composition, and a preferable lower limit is 0.05% by mass, a more preferable lower limit is 0.1% by mass, a more preferable upper limit is 15% by mass, and a more preferable upper limit is 10% by mass. The content of the (c) photopolymerization initiator is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity in photopolymerization by exposure, and 30% by mass or less from the viewpoint of sufficiently transmitting light to the bottom surface of the photosensitive resin composition (i.e., a portion away from the light source) in photopolymerization to obtain good resolution and adhesion.
(e) Other additives
The photosensitive resin composition may contain various additives in addition to the components (a) to (c) described above. Specifically, the coloring material may be, for example, a dye or a pigment. Examples of such coloring substances include phthalocyanine green, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green, basic blue 20, and adamantine green.
When the coloring material is contained, the amount of the coloring material added is preferably 0.001 to 1% by mass based on the total solid content of the photosensitive resin composition. When the amount of the coloring material added is 0.001 mass% or more, the effect of improving the handleability is obtained; when the content is 1% by mass or less, the effect of maintaining the storage stability is obtained.
In addition, a developer may be contained in the photosensitive resin composition so that a visible image can be provided by exposure. Examples of such a color-developing dye include a leuco dye and a combination of a fluoran dye and a halogen compound.
Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [ leuco crystal violet ], tris (4-dimethylamino-2-methylphenyl) methane [ leuco malachite green ], and fluoran dyes. Among these, when leuco crystal violet is used, the contrast is good, and this is preferable.
Examples of the halogen compound include n-pentyl bromide, isopentyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, dibromotoluene (benzal bromide), dibromomethane, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, n-pentyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, hexachloroethane, chlorotriazine compounds, and the like.
When these dyes are contained, the content of the dye in the photosensitive resin composition is preferably 0.1 to 10% by mass, based on the total solid content of the photosensitive resin composition.
In order to improve the thermal stability and storage stability of the photosensitive resin composition, it is preferable that the photosensitive resin composition contains a radical polymerization inhibitor or at least 1 or more compounds selected from the group consisting of benzotriazoles and carboxybenzotriazoles.
Examples of such a radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine.
Examples of the benzotriazole include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.
Examples of the carboxybenzotriazole include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, (N, N-dibutylamino) carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole.
The total amount of the radical polymerization inhibitor and the benzotriazole compound and/or carboxybenzotriazole compound is preferably 0.001 to 3% by mass, more preferably 0.05% by mass or less, and still more preferably 1% by mass or less, based on the total amount of the solid content of the photosensitive resin composition. The total addition amount is preferably 0.001 mass% or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and is preferably 3 mass% or less from the viewpoint of maintaining sensitivity.
The photosensitive resin composition may contain other plasticizers as necessary. Examples of such a plasticizer include compounds obtained by modifying bisphenol a with a polyoxyalkylene group.
Other examples of the sorbitan derivative include sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; phthalic acid esters such as diethyl phthalate; ortho-toluenesulfonamide, para-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, and the like. Particular preference is given to using sorbitan derivatives and polyalkylene glycols.
The content of the plasticizer in the photosensitive resin composition is preferably 1 to 50% by mass, more preferably 3% by mass at the lower limit and 30% by mass at the upper limit, based on the total solid content of the photosensitive resin composition. From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, it is preferably 1% by mass or more, and from the viewpoint of suppressing insufficient curing or cold flow, it is preferably 50% by mass or less.
Examples
The following examples are further specifically described, but not limited thereto.
First, methods for producing samples for evaluation in examples and comparative examples will be described, and next, methods for evaluating the obtained samples and evaluation results will be described. Here, an annular sheet is used as the roll end face protection member.
(examples 1 to 12, comparative example 1)
1. Preparation of evaluation sample
The evaluation samples in examples and comparative examples were prepared as follows.
< production of photosensitive resin laminate >
A photosensitive resin composition blend liquid was prepared by sufficiently stirring and mixing a composition 1 shown in table 1 below (wherein the number of each component represents the amount (parts by mass) of solid components, the abbreviation of which is shown in table 1 corresponds to that of table 2) and a solvent, and a 16 μm-thick polyethylene terephthalate film (R310 manufactured by Mitsubishi Plastics, inc.) was prepared as a support, and the photosensitive resin composition blend liquid was uniformly applied to the surface of the polyethylene terephthalate film by a die coater and dried, followed by forming a photosensitive resin layer. The thickness of the photosensitive resin layer was 15 μm. Next, a polyethylene film (GF-858, manufactured by ltd., TAMAPOLY co., ltd.) having a thickness of 33 μm was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated, to obtain a photosensitive resin laminate 1.
< production of photosensitive resin laminate roll >
The sheets shown in tables 3 to 5 were used as the endless sheet. For the pressure-sensitive adhesive composition containing an acrylic resin for a cyclic sheet, an adhesive composition obtained by direct use of Elleair TackNS80/SBG 85S/removability (manufactured by Elleair Texel Co., Ltd.) will be used unless otherwise specified.
For samples F and G, the adhesive compositions were adjusted as follows. That is, B-1 and M-8 shown in Table 2 were compounded so that the solid content ratio was 45:55 and 40:60, and the mixture was applied to a substrate, dried and adjusted so that the film thickness after drying was 15 μ M.
The photosensitive resin laminate 1 was cut to have a width of 495mm, and wound around an ABS resin core (core body) having an inner diameter of 77mm, an outer diameter of 88mm and a length of 530mm for 300 m. The photosensitive resin laminate wound in a roll shape had an outer diameter of 180 mm.
The photosensitive resin laminate wound around the core in a roll shape is held by a rod-shaped stainless steel holder, and the rod-shaped stainless steel holder is designed so that the other end thereof is fixed to be able to be held horizontally.
The photosensitive resin laminate was wound into a roll and covered with a cylindrical light-shielding polyethylene tube having an outer circumference of 500mm, a length of 800mm and a thickness of 80 μm.
The photosensitive resin laminate in a roll form covered with the light-shielding polyethylene tube was removed from the holder, and a roll was placed on a buffer section which was designed to have a width of 330mm and a height of 100mm and an upper portion which was curved in a concave shape so that the roll could be fixed.
One end of the light-shielding polyethylene tube is folded back to expose the end face of the rolled photosensitive resin laminate, and an annular sheet is attached. Similarly, the other end was attached with an annular sheet, and a photosensitive resin laminate roll 1 was produced.
The photosensitive resin roll 1 is packaged by folding a light-shielding polyethylene tube into a core, attaching a core holder designed so that the center portion thereof is convex and the core fits into the core.
2. Evaluation criteria
The photosensitive resin laminate roll was evaluated and rated according to the following evaluation items and evaluation criteria. The evaluation results are shown in tables 3 to 5.
(1) Removing property of foreign matter
The annular sheet was peeled from the photosensitive resin laminate roll, and it was confirmed whether or not foreign matter was attached to the annular sheet. The rating is done as follows.
○ foreign matter was attached to the annular sheet, and another adhesive tape was attached to the end face of the roll and peeled off, and no foreign matter was observed.
△ foreign matter was attached to the annular sheet, but when another adhesive tape was attached to the end face of the roll and peeled off, it was confirmed that foreign matter was also attached to the adhesive tape.
X: foreign matter is not attached to the annular sheet. When another adhesive tape was attached to the end face of the roll and peeled off, it was confirmed that foreign matter was attached.
(2) Loop sheet mountability
The roll was produced as described in the above-mentioned item < production of photosensitive resin laminate roll > and the mountability of the annular film at the end face of the roll was rated as follows.
○ the ring-shaped sheet can be simply mounted and attached to the end face of the roll without wrinkles.
△ time is required to attach and mount the loop sheet to the holder or core some of the wrinkles or air is introduced into the end of the roll.
X: the attachment and mounting of the annular sheet to the holder or the winding core requires time. When the annular sheet attached to the undesired portion is peeled off and attached again, the annular sheet is stretched and deformed or broken, and attachment to the roll end face becomes difficult.
(3) Wrapping material adhesiveness of annular sheet
After the roll was produced as described in the above-mentioned < production of photosensitive resin laminate roll > and was unsealed. After the unsealing, whether or not the annular sheet was attached to the end face was also observed in the same manner as in the attachment, and the grade was given as follows.
○, the installation is the same as the installation.
△ the ring-shaped sheet is stuck to the light-shielding cylindrical polyethylene sheet at the time of unsealing and has a part peeled from a part of the end face.
X: the ring-shaped sheet is adhered to the light-shielding cylindrical polyethylene sheet during unsealing, and is peeled off together with the light-shielding cylindrical polyethylene sheet.
(4) Removability of endless sheet
After the roll was produced as described in the above-mentioned < production of photosensitive resin laminate roll > and the roll was unsealed, the ring-shaped sheet was peeled off by a hand wearing a resin glove. The operability at the time of peeling was rated as follows.
○ the loop sheet can be easily peeled off within 5 seconds.
△ peeling of the loop sheet takes 5 seconds or more.
(5) Number of foreign matters
The photosensitive resin laminate roll of 14 rolls was produced as described in the above section < production of photosensitive resin laminate roll >. Foreign matter was removed from the end faces of all the rolls, and the foreign matter was randomly attached to the total of four positions of the roll end faces from the 14 rolls. After that, the annular sheet was attached and peeled off to all the rolls, and foreign matter adhering to the roll end face was calculated.
[ Table 1]
[ Table 2]
| B-1 | Terpolymer of 25% by mass of methacrylic acid, 50% by mass of methyl methacrylate and 25% by mass of styrene (weight-average molecular weight 50000, acid equivalent 344) |
| B-2 | Methacrylic acidTerpolymer (weight average molecular weight 70000, acid equivalent) of 25% by mass, 65% by mass of methyl methacrylate and 10% by mass of butyl acrylate 344) |
| B-3 | Terpolymer (weight average molecular weight 120000, acid equivalent) containing 25% by mass of methacrylic acid, 65% by mass of methyl methacrylate, and 10% by mass of butyl acrylate 344) |
| M-1 | Trimethylolpropane triacrylate |
| M-2 | Aminomethyl ester of hexamethylene diisocyanate and pentamethylene glycol monomethacrylate |
| M-3 | Trioxyethyl trimethylolpropane triacrylate |
| M-4 | Di (methacrylic acid) ester of polyalkylene glycol obtained by adding an average of 2 units of propylene oxide and an average of 6 units of ethylene oxide to both ends of bisphenol A |
| M-5 | Di (methacrylic acid) esters of polyethylene glycol obtained by adding ethylene oxide of 2 units on average to both ends of bisphenol A |
| M-6 | Di (methacrylic acid) ester of polyalkylene glycol obtained by adding ethylene oxide of 3 units on average to both ends of propylene oxide of 12 units on average |
| M-7 | Diacrylate of polyethylene glycol obtained from ethylene oxide having an average of 9 units |
| M-8 | Di (methacrylic acid) esters of polyethylene glycol obtained by adding ethylene oxide having an average of 5 units to each end of bisphenol A |
| I-1 | 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer |
| I-2 | 4, 4' -bis (diethylamino) benzophenone |
| D-1 | Peacock green |
| D-2 | Leuco crystal violet |
| P-1 | Para toluene sulfonamide |
| P-2 | Polypropylene glycol having a weight average molecular weight of 2000 |
| P-3 | Polyoxyethylene [ tri (1-phenylethyl) phenyl ether to which an average of 18 moles of ethylene oxide was added] |
| P-4 | Polyoxyethylene sorbitan trioleate (manufactured by Nippon emulsifier Co., Ltd., Newcol 3-85) |
| X-1 | (N, N-dibutyl)Aminoamino) carboxybenzotriazoles |
| X-2 | Triethylene glycol bis [3- (3-tert-butyl) -5-methyl-4-hydroxyphenyl]Propionic acid ester |
| X-3 | Nitrosophenylhydroxylamine aluminium salts |
| X-4 | 2-di-n-butylamino-4, 6-dithio-s-triazine |
| X-5 | 3-glycidoxypropyltrimethoxysilane |
[ Table 3]
[ Table 4]
[ Table 5]
Photosensitive resin laminate rolls were produced in the same manner as the photosensitive resin laminate roll 1 except that the photosensitive resin laminate 1 was used as photosensitive resin laminates 2 to 6 and sample B was used for the annular sheet, and the photosensitive resin laminate rolls 2 to 6 were obtained. When the evaluations (1) to (5) were performed using the photosensitive resin rolls 2 to 6, the same results as those obtained when the photosensitive resin laminate roll 1 was used were obtained.
Photosensitive resin laminate rolls were produced in the same manner as the photosensitive resin laminate roll 1 except that the photosensitive resin laminate 1 was used as photosensitive resin laminates 7 to 10, sample B was used for the annular sheet, and the outer diameter was set to 180mm as the outer diameter of 176mm, and the photosensitive resin laminate rolls 7 to 10 were obtained. The photosensitive resin laminate wound in a roll shape had an outer diameter of 176 mm. When the evaluations (1) to (5) were performed using the photosensitive resin rolls 7 to 10, the same results as those obtained when the photosensitive resin laminate roll 1 was used were obtained.
Industrial applicability
The photosensitive resin laminate roll is useful for processing precision devices and electronic materials, and is also useful as a permanent pattern to be incorporated into precision devices and electronic materials, because foreign matter can be easily removed at the time of unsealing.
Description of the reference numerals
1 photosensitive resin laminate
2 roll core
3 roll end face protection parts (Ring shaped sheet)
4 support layer
5 photosensitive resin layer
6 protective layer
7 flat plate
8 fixing part
9 light-shielding sheet
10 photosensitive resin laminate roll
Claims (25)
1. A photosensitive resin laminate roll in which a photosensitive resin laminate is wound in a roll shape around a winding core, a roll end face protection member is disposed so as to be in contact with an end face of the wound photosensitive resin laminate,
the roll end face protecting member is penetrated by the winding core,
the roll end face protection member has an adhesive composition on the side in contact with the end face of the wound photosensitive resin laminate,
the photosensitive resin laminate comprises at least a support layer and a photosensitive resin layer laminated on the support layer,
the adhesive force between the roll end face protection member and the low-density polyethylene film is 5gf/inch to 250gf/inch,
the roll end face protection member is an annular sheet,
the inner diameter of the annular sheet is 1-1.1 times of the outer diameter of the winding core.
2. The photosensitive resin laminate roll according to claim 1, which is covered with a light-shielding sheet.
3. The roll of photosensitive resin laminate according to claim 2, wherein the light-shielding sheet has a cylindrical shape.
4. The roll of photosensitive resin laminate according to claim 1,
the length of the core is longer than the width of the photosensitive resin laminate,
the roll end face protection member is an annular sheet disposed on an end face of the photosensitive resin laminate wound in a roll shape, and the annular sheet is disposed so as to penetrate through an extension portion of the winding core.
5. The photosensitive resin laminate roll according to claim 1,
the annular sheet is disposed on a horizontally extending flat plate so that a half of the annular sheet is present in the air, and H/R is 0.06-0.59 when the distance between the distal end of the annular sheet farthest from the flat plate in the portion of the annular sheet present in the air and the surface of the flat plate on the side contacting the annular sheet is defined as a bending distance H (mm) and the half of the outer diameter of the annular sheet is defined as R (mm).
6. The photosensitive resin laminate roll according to claim 1, wherein the substrate of the roll end face protection member is a non-dust paper, a low-dust paper, a synthetic paper, or a paper obtained by laminating a resin substrate with a paper.
7. The photosensitive resin laminate roll according to any one of claims 1 to 6, wherein the photosensitive resin layer is a layer containing a photosensitive resin composition containing an alkali-soluble polymer having a carboxyl group, an addition polymerizable monomer, and a photopolymerization initiator.
8. The photosensitive resin laminate roll according to claim 7, wherein the alkali-soluble polymer having a carboxyl group is a copolymer of styrene or a derivative thereof.
9. The photosensitive resin laminate roll according to claim 7, wherein the addition polymerizable monomer comprises a bisphenol A (meth) acrylate compound.
10. The roll of photosensitive resin laminate according to claim 7, wherein said photopolymerization initiator comprises hexaarylbiimidazole or a derivative thereof.
11. The photosensitive resin laminate roll according to any one of claims 1 to 6, wherein the adhesive composition contains an acrylic resin or an acrylate resin.
12. The roll of the photosensitive resin laminate according to any one of claims 1 to 6, wherein the binder composition contains a binder and particles, 50% by mass or more of the particles have a diameter of 80 to 120% of a coating thickness of the binder composition, and the content of the particles is 5 to 30 parts by weight with respect to 100 parts by weight of the binder.
13. A method for manufacturing a photosensitive resin laminate roll, characterized in that,
a photosensitive resin laminate wound in a roll shape around a winding core, and a roll end face protection member disposed so as to contact an end face of the wound photosensitive resin laminate,
the length of the core is longer than the width of the photosensitive resin laminate,
the photosensitive resin laminate comprises at least a support layer and a photosensitive resin layer laminated on the support layer,
the roll end face protecting member is penetrated by the winding core,
the roll end face protection member has an adhesive composition on the side in contact with the end face of the wound photosensitive resin laminate,
the roll end face protection member is an annular sheet material comprising: the annular sheet is integrally or divided into a plurality of parts and arranged on the end face of the rolled photosensitive resin laminate, the inner diameter of the annular sheet is 1-1.1 times of the outer diameter of the winding core after the annular sheet is arranged on the end face of the rolled photosensitive resin laminate,
the adhesive force between the annular sheet and the low-density polyethylene film is 5gf/inch to 250 gf/inch.
14. The method of manufacturing a photosensitive resin laminate roll according to claim 13, wherein the inner diameter of the annular sheet is 1.001 to 1.1 times the outer diameter of the core, and the annular sheet is disposed so as to penetrate through a protruding portion of the core.
15. A method for packaging a photosensitive resin laminate roll, characterized in that a photosensitive resin laminate roll is manufactured by the method according to claim 13 or 14, and the photosensitive resin laminate roll is further covered with a cylindrical light-shielding sheet.
16. An annular sheet for a film roll in which a film is wound around a winding core, wherein,
the length of the roll core is longer than the width of the film,
the inner diameter of the annular sheet is 1-1.1 times of the outer diameter of the winding core, and
the annular sheet is disposed so as to penetrate the winding core and is in contact with an end face of the wound film,
the annular sheet has an adhesive composition on the side contacting the end face of the wound film and is disposed on a film roll so as to penetrate the extension portion of the core,
the adhesive force between the annular sheet and the low-density polyethylene film is 5gf/inch to 250 gf/inch.
17. The annular sheet according to claim 16, wherein the film is a photosensitive resin laminate.
18. The endless sheet according to claim 16, wherein the substrate is a non-dust paper, a low-dust paper, a synthetic paper, or a paper laminated with a resin substrate.
19. The annular sheet according to claim 17 or 18, wherein the photosensitive resin layer is a layer containing a photosensitive resin composition containing an alkali-soluble polymer having a carboxyl group, an addition polymerizable monomer, and a photopolymerization initiator.
20. The loop sheet according to claim 19, wherein the alkali-soluble polymer having a carboxyl group is a copolymer of styrene or a derivative thereof.
21. The cyclic sheet according to claim 19, wherein the addition polymerizable monomer comprises a bisphenol a-based (meth) acrylate compound.
22. The cyclic sheet according to claim 19, wherein the photopolymerization initiator comprises hexaarylbiimidazole or a derivative thereof.
23. The loop sheet according to any one of claims 16 to 18, wherein the adhesive composition comprises an acrylic resin or an acrylate resin.
24. The endless sheet according to any one of claims 16 to 18, wherein said binder composition comprises a binder and particles, 50% by mass or more of said particles have a diameter of 80 to 120% of a coating thickness of said binder composition, and the content of said particles is 5 to 30 parts by weight relative to 100 parts by weight of said binder.
25. A film roll comprising the annular sheet according to any one of claims 16 to 24 covered with a light-shielding sheet.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012285697 | 2012-12-27 | ||
| JP2012-285697 | 2012-12-27 | ||
| CN201380068564.2A CN104903207B (en) | 2012-12-27 | 2013-12-26 | Photoresist duplexer is rolled up |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380068564.2A Division CN104903207B (en) | 2012-12-27 | 2013-12-26 | Photoresist duplexer is rolled up |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106966074A CN106966074A (en) | 2017-07-21 |
| CN106966074B true CN106966074B (en) | 2020-05-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710224203.2A Active CN106966074B (en) | 2012-12-27 | 2013-12-26 | Photosensitive resin laminate roll |
| CN201610799124.XA Active CN106393838B (en) | 2012-12-27 | 2013-12-26 | Photoresist laminated body is rolled up |
| CN201380068564.2A Active CN104903207B (en) | 2012-12-27 | 2013-12-26 | Photoresist duplexer is rolled up |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
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| CN201610799124.XA Active CN106393838B (en) | 2012-12-27 | 2013-12-26 | Photoresist laminated body is rolled up |
| CN201380068564.2A Active CN104903207B (en) | 2012-12-27 | 2013-12-26 | Photoresist duplexer is rolled up |
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| JP (2) | JP6046746B2 (en) |
| KR (2) | KR102191080B1 (en) |
| CN (3) | CN106966074B (en) |
| MY (1) | MY176080A (en) |
| TW (2) | TWI611990B (en) |
| WO (1) | WO2014104217A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105151562B (en) * | 2015-08-11 | 2018-07-20 | 中国乐凯集团有限公司 | A kind of packing method of optical fiber cellulose ester film |
| JP6979265B2 (en) * | 2015-10-27 | 2021-12-08 | 住友金属鉱山株式会社 | A method and a winding device for winding a long substrate, and a surface treatment device for a long substrate provided with the winding device. |
| KR20190035864A (en) * | 2016-12-07 | 2019-04-03 | 아사히 가세이 가부시키가이샤 | Photosensitive resin composition and photosensitive resin laminate |
| MY197618A (en) * | 2017-11-06 | 2023-06-28 | Asahi Chemical Ind | Photosensitive resin laminate and method for producing resist pattern |
| CN108663867A (en) * | 2018-04-11 | 2018-10-16 | 华南师范大学 | A kind of laser protective film of dyestuff doping |
| JP6735892B2 (en) * | 2018-12-13 | 2020-08-05 | 住友化学株式会社 | Package |
| JP7425978B2 (en) * | 2019-06-28 | 2024-02-01 | Tdk株式会社 | Manufacturing method for roll bodies, packaging bodies, protective films, and electronic components |
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| CN1340441A (en) * | 2000-09-01 | 2002-03-20 | 富士胶片株式会社 | Packaging method and device for photosensitive material coil and fluid heating and supplying device |
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| JP3056654U (en) * | 1998-08-10 | 1999-02-26 | ニチゴー・モートン株式会社 | Edge protection material for film roll |
| JP2001125227A (en) * | 1999-10-29 | 2001-05-11 | Konica Corp | Roll-like photosensitive material package |
| JP2001255633A (en) * | 2000-03-09 | 2001-09-21 | Konica Corp | Roll type photosensitive material package and its manufacturing method |
| JP2002099079A (en) * | 2000-09-22 | 2002-04-05 | Hitachi Chem Co Ltd | Packaged body, method of packaging photosensitive element, method of preventing edge fusion of photosensitive element, and method of preventing winding dislocation of photosensitive element |
| JP2003160175A (en) * | 2001-11-27 | 2003-06-03 | Asahi Kasei Corp | Pad for packaging |
| JP2004203430A (en) * | 2002-12-25 | 2004-07-22 | Ykk Corp | Simplified package of lengthy material roll |
| JP4196771B2 (en) | 2003-07-23 | 2008-12-17 | 日立化成工業株式会社 | ROLLED PACKING UNIT, ROLLED PACKAGE AND ROLLED PACKING METHOD |
| JP2005153909A (en) * | 2003-11-21 | 2005-06-16 | Konica Minolta Holdings Inc | Packaging element for print paper, and print paper package |
| JP4451120B2 (en) * | 2003-11-26 | 2010-04-14 | 株式会社川島製作所 | Bag package forming method and apparatus |
| EP1780599A4 (en) * | 2004-07-14 | 2010-09-01 | Asahi Kasei E Materials Corp | Photosensitive composition, pattern forming material, photosensitive laminate, pattern forming apparatus and method of pattern formation |
| JP4498058B2 (en) * | 2004-08-12 | 2010-07-07 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin laminate |
| KR101314562B1 (en) * | 2004-11-24 | 2013-10-07 | 가부시키가이샤 구라레 | Water-soluble film roll and method for paying out water-soluble film |
| JP2007133349A (en) * | 2005-10-14 | 2007-05-31 | Hitachi Chem Co Ltd | Photosensitive film roll |
| JP2007171610A (en) * | 2005-12-22 | 2007-07-05 | Fujifilm Corp | Pattern forming method |
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| CN1340441A (en) * | 2000-09-01 | 2002-03-20 | 富士胶片株式会社 | Packaging method and device for photosensitive material coil and fluid heating and supplying device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106393838B (en) | 2018-09-28 |
| TWI611990B (en) | 2018-01-21 |
| KR102191080B1 (en) | 2020-12-15 |
| JPWO2014104217A1 (en) | 2017-01-19 |
| CN106393838A (en) | 2017-02-15 |
| TWI522303B (en) | 2016-02-21 |
| WO2014104217A1 (en) | 2014-07-03 |
| KR20190018037A (en) | 2019-02-20 |
| MY176080A (en) | 2020-07-24 |
| CN106966074A (en) | 2017-07-21 |
| CN104903207A (en) | 2015-09-09 |
| KR20150079919A (en) | 2015-07-08 |
| TW201431769A (en) | 2014-08-16 |
| KR101950064B1 (en) | 2019-02-19 |
| TW201613817A (en) | 2016-04-16 |
| CN104903207B (en) | 2017-04-05 |
| JP6315724B2 (en) | 2018-04-25 |
| JP6046746B2 (en) | 2016-12-21 |
| JP2017071445A (en) | 2017-04-13 |
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