JP6095337B2 - Dry film resist roll with seal - Google Patents

Description

  The present invention relates to a dry film resist roll for use in printed circuit boards, lead frames and semiconductor packages, as well as film devices such as flexible displays, film solar cells, and film-type capacitive touch panels. The present invention relates to a dry film resist roll with a seal that does not bleed out resist at the end even when stored.

  Conventionally, in order to form a conductive pattern such as a printed wiring board, generally, a method of laminating a dry film resist on an object such as a copper clad laminate and exposing, developing and etching through a pattern mask has been carried out. Such a dry film resist is composed of a three-layer structure of a light-transmitting support film, a photosensitive layer, and a protective film. A resist pattern is formed by pressure bonding on an object, adhering a pattern mask on a light-transmitting support film, irradiating active light (usually ultraviolet rays) (exposure), and then spraying or immersing an alkaline aqueous solution or organic solvent. (Development), further remove (etch) conductive film parts such as copper foil exposed with solutions of iron chloride, copper chloride, hydrogen peroxide / sulfuric acid, alkaline ammonia, etc., and finally harden with alkaline aqueous solution or organic solvent A method of peeling the resist portion (resist peeling) has been taken.

  Such dry film resists are usually rolled into a roll and commercialized and distributed in the market. The photosensitive layer in such dry film resists has adhesiveness and fluidity and is stored. The photosensitive resin composition (resist) oozes out from the end surface of the roll, that is, edge fusion occurs (see FIG. 5), and the layers adhere to each other at the end of the roll. However, there is a problem that rewinding workability is remarkably deteriorated. In addition, the photosensitive resin composition (resist) that exudes from the end face of the roll was separated from the roll in the form of a powder or a line, and these adhered again after forming the resist pattern, resulting in foreign matter and obtained by etching There was also a problem of causing defects such as chipping in the wiring pattern and the like.

  In order to solve the occurrence of the edge fusion, in Patent Document 1 and Patent Document 2, it is proposed to cover the roll end by bringing a sheet-like desiccant into contact with the roll end of the dry film resist. It is described that the above method suppresses bleeding from the end of the photosensitive layer during winding and storage.

Japanese Patent No. 2730630 JP 2001-188319 A

  However, in the inventions described in these special documents, the effect of suppressing edge fusion cannot be said to be sufficient.

  Accordingly, an object of the present invention is to provide a dry film resist roll with a seal that solves the above-described problems and improves the edge fusion suppressing effect of the resist.

  Means for solving the problems will be described below.

The present invention includes a dry film resist roll obtained by winding a dry film resist formed by forming at least a photosensitive layer on one side of a light-transmitting support film in a roll shape, and attached to an end face of the dry film resist roll. And an end face treatment seal having adhesive properties ,
The end surface treatment seal is formed by applying an adhesive on one surface of a seal substrate,
The present invention provides a dry film resist roll with a seal having an adhesive strength of 400 to 600 g / 25 mm (conforming to JIS Z-0237) .

  In the present invention, since the end face treatment seal has adhesiveness and is attached to the end face of the dry film resist roll, the effect of suppressing the edge fusion of the resist is improved as compared with the conventional technique simply contacting the end face of the roll. did. As a result, the photosensitive resin composition (resist) that oozes from the roll end face adheres between the layers at the roll end, and the roll cannot be rewound during use, or even if the roll can be rewound, the rewinding workability is significantly deteriorated. Can be prevented. In addition, the photosensitive resin composition (resist) that exudes from the end face of the roll was separated from the roll in the form of a powder or a line, and these adhered again after forming the resist pattern, resulting in foreign matter and obtained by etching It is also possible to prevent defects such as chipping on the wiring pattern and the like.

It is an external view which shows the dry film resist roll with a seal | sticker which concerns on this invention. It is an external view which shows the dry film resist roll of FIG. FIG. 2 is an enlarged cross-sectional view of a main part of the dry film resist roll with a seal shown in FIG. It is the front view and sectional drawing which show the end surface processing seal | sticker of FIG. It is the principal part expanded sectional view which took out only 1 layer of dry film resist about the dry film resist roll which the end surface exposed.

  Hereinafter, an embodiment of a dry film resist roll with a seal according to the present invention will be described with reference to the drawings.

  A dry film resist roll 1 with a seal shown in FIG. 1 is affixed to a dry film resist roll 2 formed by winding a dry film resist 7 around a cylindrical core 8 and an end face of the dry film resist roll 2. And an end face treatment seal 3 having adhesiveness.

  Examples of the cylindrical core 8 include those made of plastic or paper having an outer diameter of about 30 to 300 mm.

<Dry film resist>
In the present invention, the dry film resist 7 constituting the dry film resist roll 2 (see FIG. 2) protected by the adhesive end face treatment seal 3 has at least the photosensitive layer 5 laminated on the translucent support film 4. (See FIG. 3). The dry film resist 7 may be selected in a range of 300 to 1000 mm in width and 100 to 500 m in length according to the application.

  The translucent support film 4 used here includes 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, and a polymethyl methacrylate copolymer. Examples include a polymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films can be stretched if necessary.

  It is preferable that the haze of the translucent support film 4 is 5.0 or less. Further, the thinner the translucent support film 4 is, the more advantageous in terms of image forming property and economic efficiency, but in order to maintain the strength, a film having a thickness of 10 to 30 μm is generally used.

  As the photosensitive resin composition constituting the photosensitive layer 5, the photosensitive resin composition is not particularly limited and a known one can be used. For example, (a) the carboxyl group content is 100 to 600 in terms of acid equivalent. And a binder resin having a weight average molecular weight of 5,000 to 500,000, (b) a photopolymerizable unsaturated compound, and (c) a photopolymerization initiator. The (a) binder resin, (b) the photopolymerizable unsaturated compound, and (c) the photopolymerization initiator may each contain one or more compounds.

  About the quantity of the carboxyl group contained in (a) resin for binders of the example of the above-mentioned photosensitive resin composition, an acid equivalent is 100-600, Preferably it is 300-400. An acid equivalent means the mass (gram) of the polymer (namely, resin for binders) which has a carboxyl group of 1 equivalent in it.

  (A) The carboxyl group in the binder resin is necessary for imparting developability and releasability to an aqueous alkali solution to the photosensitive layer. When the acid equivalent is less than 100, the development resistance is low and adversely affects the resolution and adhesion. On the other hand, when it exceeds 600, the developability and peelability are low. The acid equivalent is measured by potentiometric titration using an automatic titrator (for example, Hiranuma Auto titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.) using 0.1 mol / L sodium hydroxide.

  The weight average molecular weight of the resin for binders (a) in the example of the photosensitive resin composition described above is 5,000 to 500,000. When the weight average molecular weight exceeds 500,000, the developability is low. On the other hand, when the weight average molecular weight is less than 5,000, the tenting film strength is low and edge fuse occurs. The weight average molecular weight is preferably 10,000 to 40,000 from the viewpoint of good resolution when i-line monochromatic exposure is performed using a projection exposure machine.

  The weight average molecular weight is determined by gel permeation chromatography (for example, gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK) ( KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, using a calibration curve with polystyrene standard sample)), the weight average molecular weight (polystyrene conversion).

  (A) The binder resin in the above-described example of the photosensitive resin composition typically includes two or more monomers each selected from one or more groups selected from the group consisting of the following two types of monomers. Obtained by copolymerization.

  The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. For example, examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester.

  The second monomer is non-acidic, has one polymerizable unsaturated group in the molecule, has various properties such as developability of the photosensitive layer, resistance in etching and plating processes, and flexibility of the cured film. Chosen to retain the characteristics of Examples of such compounds include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. , 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile and the like. In a preferred embodiment of the present invention, a vinyl compound having a phenyl group (for example, styrene) is used to obtain high resolution.

  (A) The binder resin in the above-described photosensitive resin composition is a benzoyl peroxide, azoisobutyronitrile, etc. solution obtained by diluting a mixture of the above monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to synthesize by adding an appropriate amount of the radical polymerization initiator and stirring with heating. Moreover, you may synthesize | combine (a) resin for binders, adding a part of mixture to a reaction liquid dropwise. Moreover, after completion | finish of reaction, a solvent may be added and (a) binder resin may be adjusted to a desired density | concentration. Furthermore, as synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to the above solution polymerization.

  (B) The photopolymerizable unsaturated compound in the above example of the photosensitive resin composition is a polyalkylene glycol obtained by adding an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide to both ends of bisphenol A, respectively. Polymethacrylate dimethacrylate (for example, NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) with an average of 5 moles of ethylene oxide added to both ends of dimethacrylate or bisphenol A, and an average of 12 moles of propylene oxide are added. Examples include glycol dimethacrylate in which ethylene oxide is further added to the obtained polypropylene glycol and an average of 3 moles is added to both ends.

  In addition, as another example of the photopolymerizable unsaturated compound (b), a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate, and a hydroxyl group in one molecule Examples thereof include urethane compounds with compounds having a (meth) acryl group (for example, 2-hydroxypropyl acrylate, oligopropylene glycol monomethacrylate, oligoethylene glycol monomethacrylate, oligoethylenepropylene glycol monomethacrylate, etc.). Specifically, a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Blenmer PP1000), hexamethylene diisocyanate and oligoethylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Blemmer PE-) 200), a reaction product of hexamethylene diisocyanate and oligoethylenepropylene glycol monomethacrylate (manufactured by NOF Corporation, Blemmer 70PEP-350B). In the present specification, the diisocyanate residue means a residue containing a urethane bond derived from a diisocyanate compound as a raw material.

  As another example of the photopolymerizable unsaturated compound (b), an acrylate of a compound obtained by adding polypropylene glycol added with an average of 2 mol of propylene oxide and polyethylene glycol added with an average of 7 mol of ethylene oxide to nonylphenol. 4-normal nonylphenoxyheptaethylene glycol dipropylene glycol acrylate, or 4-normal nonyl phenoxy octaethylene glycol acrylate (for example, Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol added with an average of 8 moles of ethylene oxide to nonylphenol. M-114) etc. are mentioned.

  As the photopolymerizable unsaturated compound (b) in the example of the photosensitive resin composition described above, in addition to the above compounds, the following photopolymerizable unsaturated compounds may be used in combination. Examples of the compound that can be used in combination include 1,6-hexanediol di (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, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate Over DOO, bisphenol A diglycidyl ether di (meth) acrylate, and β- hydroxypropyl-beta '- (acryloyloxy) propyl phthalate.

  Next, the photopolymerization initiator (c) in the example of the photosensitive resin composition described above will be described. In the present specification, the photopolymerization initiator means a compound that is activated by various actinic rays such as ultraviolet rays and starts polymerization. The photopolymerization initiator may be a known compound.

  In a preferred embodiment, from the viewpoint of high resolution, (c) the photopolymerization initiator includes a 2,4,5-triarylimidazole dimer, and more preferably (c) the photopolymerization initiator is 2, 4,5-triarylimidazole dimer. In a more preferred embodiment, (c) the 2,4,5-triarylimidazole dimer and a benzophenone and / or a benzophenone derivative are used in combination as a photopolymerization initiator. As such a benzophenone derivative, p-aminophenyl ketone is particularly preferable from the viewpoint of sensitivity. Examples of p-aminophenyl ketone include p-aminobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p'-bis (ethylamino) benzophenone, p, p'- Examples thereof include bis (dimethylamino) benzophenone [Michler's ketone], p, p′-bis (diethylamino) benzophenone, p, p′-bis (dibutylamino) benzophenone, and the like.

  In addition to the compounds shown above, other photopolymerization initiators can be used in combination. Other photopolymerization initiators include, for example, quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether, Examples include acridine compounds such as 9-phenylacridine, benzyldimethyl ketal, and benzyldiethyl ketal. For example, combinations of thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone and tertiary amine compounds such as dimethylaminobenzoic acid alkyl ester compounds are also included. Further, oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime are also included. Furthermore, N-aryl-α-amino acid compounds can also be used, and among these, N-phenylglycine is particularly preferable.

  Moreover, in order to improve the thermal stability and storage stability of the photosensitive layer 5, it is also preferable to contain a radical polymerization inhibitor in the photosensitive resin composition. Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 Examples include '-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosamine and the like.

  Moreover, additives, such as a plasticizer, can also be contained in the photosensitive resin composition as needed. Examples of such additives include phthalic acid esters such as diethyl phthalate, p-toluenesulfonamide, polypropylene glycol, polyethylene glycol monoalkyl ether, and the like.

  Although the thickness of the photosensitive layer 5 varies depending on the application, it is usually 5 to 100 μm, preferably 5 to 50 μm, in the printed circuit board production application. The thinner the photosensitive layer 5, the better the resolution, while the thicker the photosensitive layer, the better the film strength. Therefore, the thickness of the photosensitive layer 5 may be set according to the desired resolution and film strength.

  A protective film 6 can be laminated on the photosensitive layer 5, that is, on the surface opposite to the translucent support film 4 side, if necessary. It is an important characteristic of the protective film 6 that the protective film 6 has a sufficiently small adhesive force with the photosensitive layer 5 and can be easily peeled off than the translucent support film 4. Examples of such a protective film 6 include a polyethylene film and a polypropylene film.

  The film-type capacitive touch panel manufacturing process using the dry film resist 7 can be performed by a known technique, but will be briefly described below.

  In the case where the protective film 6 is formed, first, the protective film 6 is peeled off, and then the photosensitive layer 5 is provided with a transparent conductive film layer and a light-shielding metal foil layer on both sides of the laminate for a touch panel, that is, the film substrate. It laminates by thermocompression-bonding on both metal foil surfaces of the member laminated on the whole surface.

  Next, mask films having different patterns are superimposed on both sides, and image exposure is performed with active light from both sides through the mask film.

 Next, when there is the translucent support film 4 on the photosensitive layer 5, this is removed, and subsequently, an unexposed portion of the photosensitive layer 5 is developed and removed using an alkaline aqueous solution to form a cured resist pattern. As the alkaline aqueous solution, an aqueous solution of sodium carbonate, potassium carbonate or the like can be used. These alkaline aqueous solutions are selected according to the characteristics of the photosensitive layer, but generally 0.5 to 3% by mass of sodium carbonate aqueous solution is used.

  Next, by performing known etching on the surface of the metal foil exposed by development, an image pattern of the metal foil and the transparent conductive film therebelow is formed.

  Thereafter, the cured resist pattern is peeled off with an alkaline aqueous solution that is generally stronger than the alkaline aqueous solution used in development. Although there is no restriction | limiting in particular also about the aqueous alkali solution for peeling, 1-5 mass% aqueous solution, such as sodium hydroxide and potassium hydroxide, is generally used.

  In the case of a film-type capacitive touch panel, thereafter, only the metal foil of the portion that becomes the input area of the touch panel is further etched away.

<End treatment seal with adhesiveness>
The adhesive end face treatment seal 3 has a core through hole 9 (see FIG. 4) and is attached to the end face of the dry film resist roll 2 through the core 8. When the core 8 does not protrude from the roll end surface, the end surface treatment seal 3 may not have the core through hole 9.

  The occurrence of edge fusion is affected by the moisture in the air, which is considered to be particularly large. Conventionally, efforts have been focused on suppressing the moisture permeability of the coating material itself covering the roll end surface. However, the present inventors have found that the cause of adhesion between the coating material covering the roll end surface and the roll end surface is rather large. In view of this, edge fusion can be effectively suppressed by adhering to the end face of the roll using an end face treatment seal 3 having adhesiveness so that it does not easily peel off in a state where no force is applied.

  Examples of the end-face treatment seal 3 having adhesiveness include those obtained by applying a pressure-sensitive adhesive on one surface of a seal substrate. The material is not particularly limited, and examples of the sealing substrate include dust-free paper such as polyolefin-based and polystyrene-based synthetic paper, and synthetic films such as OPP, PET, and CPP. The field where the dry film resist roll with seal of the present invention is used is often in a clean room that has been cleaned to a high level so that fine dust or dust does not cause defects in the product. When paper is used for the substrate, it is preferable to use the above-mentioned dust-free paper.

  The pressure-sensitive adhesive is not particularly limited since a known pressure-sensitive adhesive can be used. For example, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a polyether System adhesives, polyamide adhesives, fluorine adhesives, and the like. Moreover, the combination of the 1 type, or 2 or more types of adhesive selected from these adhesives may be sufficient. The adhesive force of the pressure-sensitive adhesive is preferably 300 to 700 g / 25 mm (based on JIS Z-0237). If the adhesive force is less than 300 g / 25 mm, the effect of suppressing the occurrence of edge fusion is reduced. When the adhesive force exceeds 700 g / 25 mm, the removability and the non-contamination property of the roll end surface are lowered. More preferably, it is 400-600 g / 25mm.

  As described above, since the end face treatment seal has adhesiveness and is attached to the end face of the dry film resist roll, the effect of suppressing edge fusion of the resist is improved as compared with the conventional technique in which the end face treatment seal is simply brought into contact with the end face of the roll. be able to. Therefore, the photosensitive resin composition (resist) that oozes out from the roll end face adheres between the layers at the roll end, and the roll cannot be rewound during use. Can be prevented. In addition, the photosensitive resin composition (resist) that exudes from the end face of the roll was separated from the roll in the form of a powder or a line, and these adhered again after forming the resist pattern, resulting in foreign matter and obtained by etching It is also possible to prevent defects such as chipping on the wiring pattern and the like.

  Examples of the present invention will be specifically described below.

  A dry film resist (“SUNFORT” manufactured by Asahi Kasei E-Materials Co., Ltd.) having a three-layer structure of a light-transmitting support film / photosensitive layer / protective film is wound on a vinyl chloride pipe having an outer diameter of 75 mm and a length of 300 m and a length of 300 m. A dry film resist roll having an outer diameter of 200 mm was prepared.

  Affixed to the end surface of the roll is a doughnut-shaped end surface treatment seal having an outer diameter of 200 mm and an inner diameter of 76 mm, which is obtained by applying an acrylic copolymer emulsion type adhesive on a sealing substrate made of polypropylene synthetic paper having a thickness of 30 μm. Thus, a dry film resist roll with a seal was obtained.

  The end face treatment seal used in the examples has a pressure-sensitive adhesive adhesive strength of 500 g / 25 mm (based on JIS Z-0237). When the dry film resist roll with a seal of the example was stored in a constant temperature and humidity chamber at 30 ° C. and 90% HR, the storage stability was examined, and no edge fusion occurred even after 10 days.

  The technical contents and technical features of the present invention have been disclosed as described above. However, those skilled in the art to which the present invention belongs will not depart from the technical idea of the present invention based on the teachings and disclosure of the present invention. Various substitutions and additions can be made. Accordingly, the scope of protection of the present invention is not limited to that disclosed in the examples, and includes various substitutions and additions that are not different from the present invention, and is included in the scope of the appended claims. is there.

DESCRIPTION OF SYMBOLS 1 Dry film resist roll with a seal 2 Dry film resist roll 3 End surface treatment seal 4 Light-transmitting support film 5 Photosensitive layer 6 Protective film 7 Dry film resist 8 Core core

Claims (1)

A dry film resist roll in which a dry film resist formed by forming at least a photosensitive layer on one surface of a light-transmitting support film is wound up in a roll shape, and an adhesive attached to an end face of the dry film resist roll. and a end face treatment seal having,
The end surface treatment seal is formed by applying an adhesive on one surface of a seal substrate,
The dry film resist roll with a seal | sticker whose adhesive force of the said adhesive is 400-600g / 25mm (conforms to JIS Z-0237) .

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