CN111505905A - Dry film, cured product, and electronic component - Google Patents
Dry film, cured product, and electronic component Download PDFInfo
- Publication number
- CN111505905A CN111505905A CN201911004611.2A CN201911004611A CN111505905A CN 111505905 A CN111505905 A CN 111505905A CN 201911004611 A CN201911004611 A CN 201911004611A CN 111505905 A CN111505905 A CN 111505905A
- Authority
- CN
- China
- Prior art keywords
- resin
- film
- resin layer
- protective film
- dry film
- 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.)
- Granted
Links
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- 239000011347 resin Substances 0.000 claims abstract description 149
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- 229920000647 polyepoxide Polymers 0.000 description 69
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- 239000011342 resin composition Substances 0.000 description 30
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- 239000007787 solid Substances 0.000 description 22
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- 229920003986 novolac Polymers 0.000 description 20
- 238000001723 curing Methods 0.000 description 19
- 239000011256 inorganic filler Substances 0.000 description 19
- 229910003475 inorganic filler Inorganic materials 0.000 description 19
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 16
- 229920001187 thermosetting polymer Polymers 0.000 description 16
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
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- 239000000843 powder Substances 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 3
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- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- 125000003700 epoxy group Chemical group 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
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- B32B7/03—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 with respect to the orientation of features
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- 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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- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- B32B2307/70—Other properties
- B32B2307/748—Releasability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The invention relates to a dry film, a cured product and an electronic component. [ problem ] to provide: even if the slitting process is continuously performed, the resin does not adhere to the knife and the sharpness does not deteriorate, and as a result, a dry film in which the resin at the end portion is damaged, lifted, and the protective film is lifted does not occur. [ solution ] A dry film comprising a carrier film, a resin layer, and a protective film, characterized in that the peel strength of the protective film to the resin layer is 0.010kgf/cm or more, and the peel strength of the protective film to the resin layer is greater than the peel strength of the carrier film to the resin layer.
Description
Technical Field
The invention relates to a dry film, a cured product and an electronic component.
Background
Conventionally, a dry film (laminated film) has been used as one of the methods for forming a protective film or an insulating layer such as a solder resist layer or an interlayer insulating layer provided on a printed circuit board used in an electronic device or the like (for example, patent document 1). Dry films have a resin layer obtained by applying a resin composition having desired properties onto a carrier film and then performing a drying process, and are generally distributed on the market in a state where a protective film for protecting the surface opposite to the carrier film is further laminated. The printed wiring board having the protective film and the insulating layer as described above can be manufactured by attaching (hereinafter, also referred to as "laminating") a resin layer of a dry film to a substrate, and then patterning and curing the resin layer.
When the dry film is bonded to a substrate, the protective film is removed from the resin layer, but in order not to transfer the resin composition to the protective film (hereinafter, also referred to as "accidental separation of the resin") at this time, in the conventional dry film production process, conditions are adjusted so that the peel strength of the protective film with respect to the resin composition becomes small. Patent document 2 discloses an adhesive sheet with a protective film, which does not cause resin peeling when peeling the protective film, and has a peel strength of 0.0020kgf/cm or more smaller than that of the carrier film.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-010179
Patent document 2: japanese patent No. 6353184
Disclosure of Invention
Problems to be solved by the invention
In the three-layer structure dry film having the protective film and the carrier film, a curable resin composition is usually first adjusted in viscosity according to the amount of a solvent and coated on the carrier film, and then dried in a drying furnace to form a resin layer on the carrier film, and then the protective film is laminated on the surface of the prepared dry film to produce a long dry film. The long dry film has a shape of, for example, 1m in width and 1000m in length, and is in the form of a roll.
The long dry film is formed into a dry film by slitting (cutting) to adjust the width to, for example, 50cm in accordance with the required length and width, but when slitting is continuously performed over a length of 1000m as described above, for example, in the case of the conventional dry film, resin adheres to a knife, the sharpness is deteriorated, and as a result, there is a problem that the resin is damaged and floated at the end portion, and the protective film is floated.
Accordingly, an object of the present invention is to provide: a dry film in which the resin does not adhere to the knife and the sharpness does not deteriorate even if the slitting process is continuously performed, and as a result, the resin does not break or float at the end portion, and the protective film does not float; a cured product of the resin layer of the dry film; and an electronic component having the cured product.
Means for solving the problems
The inventors have conducted intensive studies and found that: the present inventors have found that the above problems can be solved by using a dry film in which a protective film is sufficiently adhered to a resin layer and the peel strength of the protective film to the resin layer satisfies a predetermined condition, and that the transfer of a resin composition to the protective film when the protective film is removed from the resin layer, which is a concern in the past, is not possible, and thus the present invention has been completed. Namely, the dry film of the present invention comprises: the carrier film, the resin layer, and the protective film are characterized in that the peel strength of the protective film to the resin layer is more than 0.010kgf/cm, and the peel strength of the protective film to the resin layer is larger than the peel strength of the carrier film to the resin layer.
In the dry film of the present invention, the peel strength of the protective film is preferably greater than the peel strength of the carrier film to the resin layer by 0.005kgf/cm or more.
The dry film of the present invention preferably has a thickness of 60 μm or more.
In the dry film of the present invention, the protective film preferably has adhesiveness.
The cured product of the present invention is obtained by curing the resin layer of the dry film.
The electronic component of the present invention is characterized by having the cured product.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a dry film in which the resin does not adhere to the knife and the sharpness does not deteriorate even if the slitting process is continuously performed, and as a result, the resin does not break or float at the end portion, and the protective film does not float; a cured product of the resin layer of the dry film; and an electronic component having the cured product.
Drawings
FIG. 1 is a schematic sectional view schematically showing one embodiment of a dry film of the present invention.
Description of the reference numerals
11 Dry film of three-layer structure
12 resin layer
13 Carrier film
14 protective film
Detailed Description
< dry film >
A schematic cross-sectional view of a dry film of the present invention is shown in fig. 1. The three-layer dry film 11 of the present invention has a structure in which a resin layer 12 is formed on a carrier film 13 and a protective film 14 is laminated thereon. The dry film of the present invention has a three-layer structure in which the peel strength of the protective film to the resin layer is 0.010kgf/cm or more and the peel strength of the protective film to the resin layer is higher than the peel strength of the carrier film to the resin layer. Here, if the upper limit value of the peel strength of the protective film to the resin layer is, for example, 0.150kgf/cm or less, the resin composition can be favorably prevented from being transferred to the protective film.
In the dry film of the present invention, the peel strength of the protective film to the resin layer is preferably greater than the peel strength of the carrier film to the resin layer by 0.005kgf/cm or more. Here, if the upper limit of the difference in peel strength is, for example, 0.150kgf/cm or less, the resin composition can be favorably prevented from being transferred to the protective film.
The dry film of the present invention satisfies the above-described characteristics, and therefore, even if slitting is continuously performed, the resin does not adhere to a knife and the sharpness does not deteriorate, and as a result, breakage, floating of the resin and floating of the protective film at the end portions do not occur. Such an effect is remarkable in a dry film having a thickness of 60 μm or more, further remarkable in a dry film having a thickness of 100 μm or more, and particularly remarkable in a dry film having a thickness of 150 μm or more. The upper limit of the thickness of the dry film is 500. mu.m.
[ protective film ]
The protective film is provided on the surface of the resin layer opposite to the carrier film for the purpose of preventing adhesion of dust or the like to the surface of the resin layer of the dry film, and for the purpose of preventing physical damage to the surface of the resin layer during slitting of the dry film and improving handling properties. Examples of the material used for the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as PET and PEN, polycarbonates, and polyimides.
As the protective film of the present invention, any commercially available protective film may be used as long as it satisfies the characteristics of the present invention that the peel strength of the protective film to the resin layer is 0.010kgf/cm or more and the peel strength of the protective film to the resin layer is larger than the peel strength of the carrier film to the resin layer, and the peel strength of the protective film is increased by adjusting the pressure and temperature at the time of lamination, for example, conventional films such as biaxially stretched polypropylene films MA-411, MA-420 and MAM-430 manufactured by OjiF-Tex Co., ltd, and thereby the peel strength of the protective film can be increased, and preferable films include heat-resistant micro-adhesive special polyester films T-10 manufactured by Futamura Chemical Co., L td., heat-resistant micro-adhesive special polyester films T-685 series manufactured by Nitto Shinko Corporation, Somatac WA series (PS-WA 105, PS-1080, PS-503, PS-DNa series, PSDNa-DNa-300M manufactured by Futamura Chemical Co., and Nitto Shinko Corporation, a Corporation, heat-resistant micro-adhesive special polyester films T-685 series (PS-WA series, PSATCA), heat-adhesive special polyester films manufactured by Somatac series, PSATCA series, PSD series, PSADN series films manufactured by Somar K-.
Here, the peel strength of the protective film to the resin layer in the present invention is a peel strength (90 ° peel strength) when the protective film is peeled from the resin layer in a direction perpendicular to the resin layer (90 ° direction), and can be determined by measuring the peel strength when the protective film is peeled from the resin layer at a peel angle of 90 ° using a tensile tester. The tensile tester includes, for example, a universal tensile tester AG-X manufactured by Shimadzu corporation.
When the protective film is bonded to the resin layer, the protective film is preferably laminated on the resin layer by a roller, pressure bonding, or the like under a temperature condition of about the lowest melting temperature of the curable resin composition. The pressure of the pressure in the lamination treatment is preferably 0.01kgf/cm2～20kgf/cm2. Here, the definition of the lowest melting temperature is as follows.
< definition of minimum melting temperature >
The prepared dry film (40 μm) was subjected to vacuum laminator MV L P-500 (manufactured by Co., Ltd.), sample for measuring melt viscosity with a thickness of 200 μm and a size of 50 × 50mm was prepared under conditions (temperature 50 ℃, time 120 seconds, pressure 0.5MPa, peeling protective film surface), then processed into a circular shape with a measured size φ 20mm, and PET film on the front and back surfaces was peeled off to prepare a sample for measurement, and then measured by rheometer HAAKE MARS40 (manufactured by Thermo Fisher) under the following conditions, and the melt viscosity was measured according to the viscosity definition at that time, and measured by an oscillation mode of transducer φ parallel plate 20mm, strain 2%, frequency 1Hz, gap 180 μm of the sample, and temperature raising method of 5 ℃/min from room temperature, and defined by the temperature at which the viscosity of the material becomes the lowest.
Here, in order to increase the peel strength of the protective film to the resin layer to the greatest extent possible within the range of the present invention while using a protective film having no micro-adhesiveness, the bonding temperature must be higher than the conventional bonding temperature, but in the above case, when unevenness occurs in the bonding temperature, or when the bonding temperature becomes excessively high, there is a problem as follows: the problem of stretching of the protective film, and the problem of curling due to the difference in shrinkage rates between the protective film and the resin layer and between the protective film and the carrier film during shrinkage after bonding. Therefore, in the present invention, a protective film having adhesiveness such as a micro-adhesive protective film is preferably used because the peel strength of the protective film can be improved without increasing the bonding temperature. As a material constituting the adhesive layer of the protective film having adhesiveness, a styrene polymer or a styrene-isoprene polymer is preferable.
In addition, as the protective film, a biaxially stretched polypropylene film is preferably used from the viewpoint that the cooling shrinkage after lamination of the resin layer can be reduced.
The thickness of the protective film is not particularly limited, and may be appropriately selected within a range of approximately 10 to 100 μm depending on the application. The surface of the protective film on which the resin layer is provided is preferably subjected to a treatment for improving adhesion, such as embossing, corona treatment, or micro-adhesion treatment, or a mold release treatment.
[ resin layer ]
The resin layer of the dry film of the present invention is generally in a state referred to as a B-stage state and is obtained from a curable resin composition, specifically, a curable resin composition is applied to a film and then subjected to a drying step. The thickness of the resin layer is not particularly limited, and may be, for example, 1 to 200 μm. In the present invention, since flatness is more excellent when the thickness is large, for example, a thickness of 30 μm or more, further 50 μm or more, and further 100 μm or more can be suitably used. A plurality of resin layers of the dry film of the present invention may be stacked to form a resin layer having a thickness of more than 200 μm. In this case, a roll laminator or a vacuum laminator may be used.
The resin layer preferably contains a curable resin, and may contain an epoxy resin, for example. The epoxy resin is a resin having an epoxy group, and any conventionally known one may be used. There may be mentioned: a 2-functional epoxy resin having 2 epoxy groups in the molecule, a polyfunctional epoxy resin having 3 or more epoxy groups in the molecule, and the like. The epoxy resin may be hydrogenated. The resin layer contains at least 1 of a semi-solid epoxy resin and a crystalline epoxy resin as the epoxy resin. The semi-solid epoxy resin and the crystalline epoxy resin may be used alone in 1 kind or in combination of 2 or more kinds. The resin layer may contain a solid epoxy resin or a liquid epoxy resin. In the present specification, a solid epoxy resin means an epoxy resin which is solid at 40 ℃, a semi-solid epoxy resin means an epoxy resin which is solid at 20 ℃ and liquid at 40 ℃, and a liquid epoxy resin means an epoxy resin which is liquid at 20 ℃. The determination of the liquid state is performed according to "method for confirming liquid state" of "province of the year" No. 1 "attached to the test and property of the dangerous object. For example, the method is described in paragraphs 23 to 25 of Japanese patent application laid-open No. 2016-079384. The crystalline epoxy resin means an epoxy resin having high crystallinity, and means a thermosetting epoxy resin having a polymer chain regularly arranged at a temperature of not more than the melting point and having a low viscosity equivalent to that of a liquid resin when melted, although it is a solid resin.
Examples of the semi-solid epoxy resin include bisphenol A type epoxy resins such as EPIC L ON860, EPIC L ON900-IM, EPIC L ONEXA-4816, EPIC L ON EXA-4822, Epototo YD-134, manufactured by Tokyo chemical Co., Ltd, jER834, jER872, and E L A-134, manufactured by Sumitomo chemical Co., Ltd, naphthalene type epoxy resins such as EPIC L ON HP-4032, manufactured by DIC corporation, and phenol novolak type epoxy resins such as EPIC L ON N-740, manufactured by DIC corporation.
As the semi-solid epoxy resin, at least one selected from the group consisting of a bisphenol a type epoxy resin, a naphthalene type epoxy resin, and a phenol novolac type epoxy resin is preferably contained. By including the semi-solid epoxy resin, the glass transition temperature (Tg) of the cured product becomes high, the CTE becomes low, and the crack resistance is excellent.
As the crystalline epoxy resin, for example, a biphenyl type epoxy resin, such as JeR YX4000, JerYX4000H, JeR Y L6121H, JeR Y L6640, JeR Y L6677 manufactured by Mitsubishi chemical corporation, for example, a diphenyl sulfide type epoxy resin, such as EPTOTO YS L V-120TE manufactured by Tokyo chemical Co., Ltd, a phenylene type epoxy resin, such as EPTOTOTO YDC-1312 manufactured by Tokyo chemical corporation, a naphthalene type epoxy resin, such as EPIC L ONHP-4032 and EPIC L ON HP-4032D, EPIC L ON HP-4700 manufactured by DIC corporation, can be used, and as the crystalline epoxy resin, such as EPTOYS L V-90C manufactured by Tokyo chemical corporation, TETOYS L V-90C manufactured by TETOS-isocyanurate manufactured by Chinesis used.
Examples of the solid epoxy resin include naphthalene type epoxy resins such as HP-4700 (naphthalene type epoxy resin) manufactured by DIC corporation, EXA4700 (4-functional naphthalene type epoxy resin) manufactured by DIC corporation, and NC-7000 (naphthalene skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kabushiki Kaisha, epoxy resins (trisphenol type epoxy resins) of condensates of phenols such as EPPN-502H (trisphenol epoxy resins) and aromatic aldehydes having a phenolic hydroxyl group, dicyclopentadiene aralkyl type epoxy resins such as EPIC 26 ON HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resins) manufactured by Nippon Kabushiki Kaisha, biphenyl aralkyl type epoxy resins such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resins) manufactured by Nippon Kabushiki Kaisha, biphenyl/phenol type epoxy resins such as EPArabic No. L, bisphenol/phenol type epoxy resins such as NC-L ONN, IC 35N 690, TEN-L, TEN-35 manufactured by Nippon Kabushiki Kaisha, epoxy resin, and the like, and the epoxy resins manufactured by Nippon Kabushiki Kaisha, and the like, and the epoxy resins are excellent in heat resistance, and the like, and the epoxy.
Examples of the liquid epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl catechol type epoxy resin, glycidyl amine type epoxy resin, aminophenol type epoxy resin, and alicyclic epoxy resin. By containing the liquid epoxy resin, the flexibility of the dry film is excellent.
The amount of the semi-solid epoxy resin and the crystalline epoxy resin is preferably 5 to 40% by mass, more preferably 10 to 30% by mass in total, based on the total amount of the epoxy resin. When the amount is within the above range, the tackiness and flexibility of the resin layer of the dry film are excellent.
[ inorganic Filler ]
The resin layer preferably contains an inorganic filler, and the cured product obtained can be inhibited from curing shrinkage by compounding the inorganic filler, thereby improving the adhesion, hardness, and thermal characteristics such as crack resistance caused by the thermal strength of a conductor layer such as copper located around an insulating layer, and the inorganic filler can be a conventionally known inorganic filler, and is not limited to a specific substance, and examples thereof include silica such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, and spherical silica, talc, clay, nonisburg silica particles, boehmite, magnesium carbonate, calcium carbonate, titanium oxide, alumina, aluminum hydroxide, silicon nitride, aluminum nitride, calcium zirconate, and other bulk pigments, metal powders such as copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold, and platinum, the inorganic filler is preferably spherical CTE particles, among which silica is preferable, the cured product of the curable composition is inhibited from curing shrinkage, and is made to be lower, the characteristics such as adhesion and hardness are improved, and the inorganic filler having a large specific gravity, such as alumina, is generally accelerated from the viewpoint of the sedimentation rate of the inorganic filler, and the average particle size of the inorganic filler can be determined by the laser diffraction method of the inorganic filler, such as the average particle size No. 3.
The aforementioned inorganic filler may be surface-treated. As the surface treatment, surface treatment without introducing an organic group such as surface treatment with a coupling agent, alumina treatment, or the like may be performed. The surface treatment method of the inorganic filler is not particularly limited, and a known conventional method may be used, and the surface of the inorganic filler may be treated with a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group.
The inorganic filler may be mixed with an epoxy resin or the like in a powder or solid state, or may be mixed with a solvent or a dispersant to form a slurry and then mixed with an epoxy resin or the like.
The inorganic filler may be used alone in 1 kind, or may be used in the form of a mixture of 2 or more kinds. The amount of the inorganic filler is preferably 10 to 90 mass%, more preferably 50 to 90 mass%, and still more preferably 60 to 90 mass%, based on the total solid content of the resin layer of the dry film. When the amount of the inorganic filler is 10% by mass or more, thermal expansion is suppressed and heat resistance is improved, while when it is 90% by mass or less, generation of cracks can be suppressed.
[ curing agent ]
The resin layer preferably contains a curing agent. Examples of the curing agent include compounds having a phenolic hydroxyl group, polycarboxylic acids and anhydrides thereof, compounds having a cyanate group, compounds having an active ester group, compounds having a maleimide group, alicyclic olefin polymers, and the like. The curing agent may be used alone in 1 kind or in combination of 2 or more kinds.
In the present invention, the resin layer preferably contains at least 1 of a compound having a phenolic hydroxyl group, a compound having an active ester group, a compound having an isocyanate group, and a compound having a maleimide group. By using a compound having a phenolic hydroxyl group and a compound having an active ester group, a cured product having excellent adhesion to a substrate having low roughness or a circuit can be obtained. Further, the use of cyanate ester increases Tg of the cured product and improves heat resistance, and the use of a compound having a maleimide group increases Tg of the cured product and improves heat resistance, and the CTE can be reduced.
As the compound having a phenolic hydroxyl group, conventionally known compounds such as phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, cresol/naphthol resin, polyvinyl phenol, phenol/naphthol resin, phenol resin having α -naphthol skeleton, cresol novolak resin having triazine skeleton, biphenyl aralkyl type phenol novolak resin, Xylok type phenol novolak resin and the like can be used.
Among the compounds having a phenolic hydroxyl group, those having a hydroxyl equivalent of 100g/eq or more are preferred, and examples of the compounds having a phenolic hydroxyl group having a hydroxyl equivalent of 100g/eq or more include dicyclopentadiene skeleton phenol novolak resin (GDP series, product of seiko chemical corporation), Xylok-type phenol novolak resin (MEH-7800, product of meihua chemical corporation), biphenyl aralkyl-type novolak resin (MEH-7851, product of meihua chemical corporation), naphthol aralkyl-type curing agent (SN series, product of seiki gill corporation), triazine skeleton-containing cresol novolak resin (L a-3018-50P, DIC), triazine skeleton-containing phenol novolak resin (L a-705N, DIC), and the like.
The compound having an isocyanate group is preferably a compound having 2 or more isocyanate groups (-OCN) in one molecule. Any conventionally known compound can be used as the compound having a cyanate group. Examples of the compound having a cyanate group include phenol novolac type cyanate ester resin, alkylphenol novolac type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol a type cyanate ester resin, bisphenol F type cyanate ester resin, and bisphenol S type cyanate ester resin. In addition, a prepolymer in which a part of the prepolymer is triazinated may be used.
Examples of commercially available compounds having a cyanate group include phenol novolak type polyfunctional cyanate ester resins (L naza Japan L td, PT30S), prepolymers (L naza Japan L td, BA230S75) in which a part or all of bisphenol A dicyanate is triazined to form a trimer, and cyanate ester resins (L naza Japan L td, DT-4000, DT-7000) containing a dicyclopentadiene structure.
The compound having an active ester group is preferably a compound having 2 or more active ester groups in one molecule, and the compound having an active ester group can be usually obtained by a condensation reaction of a carboxylic acid compound and a hydroxyl compound, and among these, a compound having an active ester group obtained by using a phenol compound or a naphthol compound as a hydroxyl compound is preferably used.
As commercially available compounds having an active ester group, dicyclopentadiene type diphenol compounds, such as HPC8000-65T (available from DIC), HPC8100-65T (available from DIC), and HPC8150-65T (available from DIC), may be mentioned.
The compound having a maleimide group is a compound having a maleimide skeleton, and any conventionally known compound can be used. The compound having a maleimide group preferably has 2 or more maleimide skeletons, more preferably N, N ' -1, 3-phenylenedimaleimide, N ' -1, 4-phenylenedimaleimide, N ' -4, 4-diphenylmethane bismaleimide, 1, 2-bis (maleimide) ethane, 1, 6-bismaleimide hexane, 1, 6-bismaleimide- (2,2, 4-trimethyl) hexane, 2 ' -bis- [4- (4-maleimidophenoxy) phenyl ] propane, 3 ' -dimethyl-5, 5 ' -diethyl-4, 4 ' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylenebismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bisphenol A diphenyl ether bismaleimide, polyphenylmethane maleimide, and oligomers thereof, and a diamine condensate having a maleimide skeleton. The oligomer is obtained by condensing a compound having a maleimide group as a monomer among the compounds having a maleimide group.
Examples of commercially available compounds having a maleimide group include BMI-1000(4,4 '-diphenylmethane bismaleimide, manufactured by Daihu Kasei Kogyo Co., Ltd.), BMI-2300 (phenylmethane bismaleimide, manufactured by Daihu Kasei Kogyo Co., Ltd.), BMI-3000 (m-phenylene bismaleimide, manufactured by Daihu Kasei Kogyo Co., Ltd.), BMI-5100(3, 3' -dimethyl-5, 5 '-dimethyl-4, 4' -diphenylmethane bismaleimide, manufactured by Daihu Kasei Kogyo Co., Ltd.), BMI-7000 (4-methyl-1, 3-phenylene bismaleimide, manufactured by Daihu Kasei Kogyo Co., Ltd.), BMI-TMH ((1, 6-bismaleimide-2, 2, 4-trimethyl) hexane, Manufactured by Dazai chemical industry Co., Ltd.) and the like.
The amount of the curing agent is preferably 20 to 100 parts by mass, more preferably 25 to 90 parts by mass, per 100 parts by mass of the epoxy resin.
Specific examples of the curable resin composition for forming the resin layer include, but are not limited to, a thermosetting resin composition, a photocurable and thermosetting resin composition containing a photopolymerization initiator, a photocurable and thermosetting resin composition containing a photobase generator, a photocurable and thermosetting resin composition containing a photoacid generator, a negative photocurable and thermosetting resin composition, a positive photosensitive and thermosetting resin composition, an alkali development photocurable and thermosetting resin composition, a solvent development photocurable and thermosetting resin composition, a swelling and peeling thermosetting resin composition, and a dissolving and peeling thermosetting resin composition.
In the following, as an example, a case where a resin layer is formed from a thermosetting resin composition containing no photocurable component will be described with respect to components that can be contained in addition to the above components.
The resin layer may contain a thermosetting resin other than an epoxy resin, and for example, the following resin may be used: known and conventional thermosetting resins such as isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, polyfunctional oxetane compounds, episulfide resins, and the like.
The resin layer may further contain a thermoplastic resin in order to improve the mechanical strength of the resulting cured film. The thermoplastic resin is preferably soluble in a solvent. When the resin is soluble in a solvent, the flexibility of the dry film is improved, and the generation of cracks and powder falling can be inhibited. Examples of the thermoplastic resin include a thermoplastic polyhydroxypolyether resin, a phenoxy resin which is a condensate of epichlorohydrin and various 2-functional phenol compounds, a phenoxy resin in which the hydroxyl group of a hydroxyether moiety present in the skeleton thereof is esterified with various acid anhydrides and/or acid halides, a polyvinyl acetal resin, a polyamide resin, a polyamideimide resin, and a block copolymer. The thermoplastic resin may be used alone in 1 kind or in combination of 2 or more kinds.
The resin layer contains a polymer resin. The glass transition point of the polymer resin is preferably-40 to 20 ℃, more preferably-15 to 15 ℃, and particularly preferably-5 to 15 ℃. When the temperature is-5 to 15 ℃, the warpage of the cured product can be suppressed well.
The higher the weight average molecular weight of the polymer resin, the greater the effect of preventing the inorganic filler from settling, and therefore, it is preferably 10 ten thousand or more, more preferably 20 ten thousand or more. The upper limit value is, for example, 100 ten thousand or less.
Examples of the polymer resin include polymer resins having 1 or more kinds of skeletons selected from a butadiene skeleton, an amide skeleton, an imide skeleton, an acetal skeleton, a carbonate skeleton, an ester skeleton, a urethane skeleton, an acrylic skeleton and a siloxane skeleton, and examples thereof include polymer resins having a butadiene skeleton (manufactured by Nippon Cao Kao K.K. "G-1000", "G-3000", "GI-1000", "GI-3000", manufactured by Kao "R-45 EPI", manufactured by Daicel chemical Industries, L td., manufactured by "PB 3600", "EPFD AT 501", manufactured by Clay Valley Corporation "Ricon 130", "Ricon 142", "Ricon 150", "Ricon 657", "Ricon 130 MA"), polymer resins having a butadiene skeleton and a polyimide skeleton (described in Japanese patent application laid-open publication No. 2006 37083), polymer resins having an acrylic skeleton (manufactured by Nagase Corporation "cheeX 3", "SG-P600L B-280", "SG-280 SG-AS-790", manufactured by "SA 2K-2000", and "SG-3000K-2000K", manufactured by "SA 50 and" SA ", respectively.
The amount of the thermoplastic resin is preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the resin layer. When the amount of the thermoplastic resin is within the above range, a uniform rough surface state can be easily obtained.
Further, the resin layer may contain rubber-like particles as needed. Examples of such rubber-like particles include polybutadiene rubber, polyisopropylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, carboxyl-modified polybutadiene rubber, acrylonitrile-butadiene rubber modified with a carboxyl group or a hydroxyl group, and crosslinked rubber particles and core-shell rubber particles thereof, and 1 or more may be used alone or 2 or more may be used in combination. These rubber-like particles are added for the purpose of improving flexibility of the obtained cured film, improving crack resistance, enabling surface roughening treatment with an oxidizing agent, and improving adhesion strength to a copper foil or the like.
The average particle diameter of the rubber-like particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 1 μm. The average particle diameter of the rubber-like particles of the present invention can be determined by a laser diffraction type particle diameter distribution measuring apparatus. For example, the rubber-like particles can be measured by uniformly dispersing the rubber-like particles in an appropriate organic solvent by ultrasonic waves or the like, preparing a particle size distribution of the rubber-like particles on a mass basis using Nanotracwave manufactured by Nikkiso K.K., and setting the median particle size as an average particle size.
The amount of the rubber-like particles is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on the total solid content of the resin layer. When the amount is 0.5% by mass or more, crack resistance can be obtained, and the adhesion strength to a conductor pattern or the like can be improved. When the amount is 10% by mass or less, the Coefficient of Thermal Expansion (CTE) decreases, the glass transition temperature (Tg) increases, and the curing properties improve.
The resin layer may contain a curing accelerator. The curing accelerator is a substance that accelerates a thermosetting reaction, and is used to further improve properties such as adhesion, chemical resistance, and heat resistance. Specific examples of such a curing accelerator include imidazole and its derivatives; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylsulfone, dicyandiamide, urea derivatives, melamine, and polyhydrazide; organic acid salts and/or epoxy adducts thereof; an amine complex of boron trifluoride; triazine derivatives such as ethyldiamino-s-triazine, 2, 4-diamino-s-triazine, and 2, 4-diamino-6-xylyl-s-triazine; amines such as trimethylamine, triethanolamine, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4, 6-tris (dimethylaminophenol), tetramethylguanidine, and m-aminophenol; polyphenols such as polyvinyl phenol, polyvinyl phenol bromide, phenol novolac, and alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2, 5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the foregoing polybasic acid anhydrides; photocationic polymerization catalysts such as diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4, 6-triphenylthiopyrylium hexafluorophosphate and the like; styrene-maleic anhydride resin; an equimolar reaction product of phenyl isocyanate and dimethylamine, an equimolar reaction product of organic polyisocyanate such as toluene diisocyanate or isophorone diisocyanate and dimethylamine, and a conventionally known curing accelerator such as a metal catalyst. Among the curing accelerators, phosphonium salts are preferred in view of obtaining resistance to BHAST (applied high accessed Stress test).
The curing accelerator may be used singly or in combination of 2 or more. The curing accelerator is not essential, but may be used in an amount of preferably 0.01 to 5 parts by mass per 100 parts by mass of the epoxy resin when it is particularly desired to accelerate curing. In the case of the metal catalyst, the amount is preferably 10 to 550ppm, more preferably 25 to 200ppm in terms of metal, per 100 parts by mass of the compound having an isocyanate group.
Examples of the organic Solvent include, but are not limited to, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like, specifically, ketones such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone, methyl isobutyl ketone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, and the like, esters such as ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, and the like, alcohols such as ethanol, propanol, 2-methoxypropanol, N-butanol, isobutanol, isoamyl alcohol, ethylene glycol, propylene glycol, and the like, aliphatic hydrocarbons such as octane, decane, petroleum ether, naphtha, hydrogenated naphtha, Solvent naphtha, and the like, and also, and N, N-dimethyl formamide (Toxol, Sporo ethanol, Spodo ethanol, Sphingol, Spodol, and the Solvent # 39150, and the like, and the Solvent # 3,29, SWO 3, SWA # 3, SWO, SWA 3, SWA # 3, SWA.
The amount of the residual solvent in the resin layer is preferably 0.5 to 7.0 mass%. When the residual solvent is 7.0 mass% or less, bumping during thermal curing is suppressed, and the surface flatness becomes better. Further, excessive decrease in melt viscosity and resin flow can be suppressed, and flatness can be improved. When the residual solvent is 0.5% by mass or more, the fluidity at the time of lamination is good, and the flatness and embeddability become better.
The resin layer may further contain, as required, conventionally known coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black, conventionally known thickeners such as asbestos, ORBEN, BENTON and fine powder silica, antifoaming agents and/or leveling agents such as silicone-based, fluorine-based and polymer-based agents, adhesion imparting agents such as thiazole-based, triazole-based and silane coupling agents, flame retardants, and conventionally known additives such as titanate-based and aluminum-based agents.
[ Carrier film ]
The carrier film is a film having a function of supporting the resin layer of the dry film, and is a film to which a curable resin composition is applied when forming the resin layer. As the carrier film, for example, a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a film made of a thermoplastic resin such as a polyimide film, a polyamideimide film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film or a polystyrene film, a surface-treated paper, or the like can be used. Among them, a polyester film can be suitably used from the viewpoint of heat resistance, mechanical strength, handling property, and the like. The thickness of the carrier film is not particularly limited, and is appropriately selected within a range of approximately 10 to 150 μm depending on the application. The surface of the carrier film on which the resin layer is provided may be subjected to a release treatment. Further, a sputtered or ultra-thin copper foil may be formed on the surface of the carrier film on which the resin layer is provided.
As a method for manufacturing a printed wiring board using the dry film of the present invention, a conventionally known method may be used. For example, when the resin layer is formed of a thermosetting resin composition, a printed wiring board can be manufactured by the following method. The protective film is peeled off from the dry film, and after being heat-laminated on the circuit board on which the circuit pattern is formed, it is thermally cured. The heat curing may be carried out in an oven or under hot plate pressure. When the substrate having the circuit formed thereon is laminated with the dry film of the present invention or pressed with a hot plate, a copper foil or a substrate having the circuit formed thereon may be simultaneously laminated. A printed wiring board can be manufactured by forming a pattern or a via hole by laser irradiation or drilling at a position corresponding to a predetermined position on a base material on which a circuit pattern is formed, and exposing a circuit wiring. At this time, when a component (smear) remaining without being completely removed is present on the circuit wiring in the pattern and the via hole, the desmear process is performed. The carrier film may be peeled at any time after lamination, after heat curing, after laser processing, or after desmear treatment. The interlayer circuit may be connected by a copper post.
The dry film of the present invention can be preferably used for the formation of a permanent protective film of an electronic part, particularly a printed circuit board, and particularly can be preferably used for the formation of a solder resist layer, an interlayer insulating layer, a coverlay layer of a flexible printed circuit board. In particular, the dry film of the present invention can be preferably used for the purpose of forming a cured product having a large content of the inorganic filler. Wiring can be attached using the dry film of the present invention to form a wiring board. Further, the resin composition can be used as a sealing material for semiconductor chips.
Examples
The present invention will be specifically described below by way of examples and comparative examples thereof, but the present invention is not limited to the following examples. In the following, the terms "part" and "%" are based on mass unless otherwise specified.
< preparation of curable resin composition >
The materials described in tables 1 and 2 and the solvent were placed in a vessel, and stirred while heating to 50 ℃, and then the resin and the coupling agent were added, respectively. After confirming that the resin was dissolved, the filler component was added and sufficiently stirred. Then, the mixture was kneaded by a three-roll mill to prepare curable resin compositions 1 to 4.
< preparation of Dry film >
The amount of the solvent is adjusted so that the viscosity of the obtained curable resin composition is 0.5 to 20 dPa.s (rotational viscometer 5rpm, 25 ℃), and the resin layer is coated on a carrier film (PET film; TN-100 manufactured by Toyo Boseki K., thickness 38 μm) by using HIRANO TECSHEED CO., (lTtT translation = L "" & (gTt L &) lTt/T & (gTt TD.) Standard L ab Coater so that the film thickness of the resin layer becomes 40 μm after drying, and then the resin layer is dried in a drying oven provided with a temperature gradient at 80 to 100 ℃ so that the residual solvent in the resin layer becomes 0.5 to 2.5 mass%, and the resin layer is formed on the carrier film, and then the roll surface temperature is 110 ℃ and the pressure is 0.1kgf/cm2The surface of the prepared dry film was coated with the protective films (Oji F-Tex Co., ltd. OPP films MA-411 and Futamur) shown in the tablea self-adhesive OPP film 100M manufactured by Chemical Co., L td., or a heat-resistant micro-adhesive special polyester film T-APN10 manufactured by Nitto Shinko corporation) was laminated to prepare a roll-like dry film having a three-layer structure of 1000M in amount of examples 1 to 6 and comparative example 1.
Specifically, comparative example 1 was prepared by bonding a protective film onto a curable resin composition under normal bonding temperature conditions using a protective film MA-411 having no adhesiveness. On the other hand, example 1 was prepared by using the same non-adhesive protective film MA-411 and setting the bonding temperature of the protective film higher than the normal bonding temperature condition, and further, examples 2 to 6 were prepared by using the protective film 100M and T-APN10 having adhesive properties instead of the non-adhesive protective film MA-411.
< measurement of peeling Strength >
For the obtained three-layer structured dry film, (a) the peel strength of the carrier film to the resin layer and (B) the peel strength of the protective film to the resin layer were measured. The obtained dry film was fixed to FR4 having a thickness of 1.6mm by an adhesive, and a notch having a width of 10mm and a length of 150mm was formed in the surface of the film, and one end of the film was peeled off. Thereafter, the film was clamped at its end and fixed by a jig, and the peel strength was measured by a universal tensile tester AG-X manufactured by Shimadzu corporation. The test method was carried out at a temperature of 25 ℃ and a peel angle of 90 ℃ at a speed of 50 mm/min in accordance with JIS-C-6481. The measurement results are shown in table 3.
< evaluation of separation of resin >
The obtained roll-like dry film having a three-layer structure was slit continuously by 1000m by an automatic cutter device TS-350P (manufactured by BAYOU IRON WORKS Co., Ltd.), and the state of the resin end of the slit was evaluated. The evaluation criteria are as follows. The evaluation results are shown in table 3.
Good: the resin end was not damaged or the protective film was not peeled off even after processing 1000 m.
× breakage and peeling of the protective film (lifting of about 3 mm) were observed at the resin end after processing 1000 m.
< evaluation of transfer of resin composition (unexpected separation of resin) >
The prepared long 3-layer dry film (a roll product having a thickness of 40 μ M, a width of 490mm and a length of 100M) was placed in an automatic cutting laminator H L M-A60-T (manufactured by Hitachi chemical Co., Ltd.), the protective film was peeled off by a take-up roll, and then 20 sheets of copper clad laminate having a size of 500 × 500mm and a thickness of 0.8mm were temporarily attached continuously at a lamination speed of 1M/min, a roll temperature of 90 ℃ and a roll pressure of 0.2MPa, and experiments were carried out with the evaluation standards set as follows, and the evaluation results are shown in Table 3.
Good: the wound portion of the protective film between the wound and temporarily bonded (thermocompression bonded) portions of the protective film was not confirmed to be separated from the resin layer.
× separation of the resin layer was confirmed in the wound portion of the protective film.
[ Table 1]
[ Table 2]
＊ 1 EPIC L ON840 (liquid epoxy resin, epoxy equivalent 185g/eq) available from DIC corporation
＊ 2 EPIC L ON860 (bisphenol A type solid epoxy resin, epoxy equivalent 245g/eq) manufactured by DIC corporation
＊ 3 EPIC L ON HP-5000 (naphthalene skeleton-modified polyfunctional epoxy resin, epoxy equivalent 252g/eq) manufactured by DIC corporation
＊ 4 HF-1M, phenol novolac resin, hydroxyl equivalent 106g/eq, manufactured by Minghe Kaishi Kabushiki Kaisha
＊ 5 EPIC L ONHPC-8000 manufactured by DIC corporation, active ester resin, active equivalent 223g/eq, solid state
＊ 6 dimethylaminopyridine
＊ 7 2E4MZ, 2-ethyl-4-methylimidazole manufactured by Siguohuako K.K.
＊ 8 phenoxy resin,
＊ 9 SO-C1 (ADMATECHS COMPANY), spherical silica, and 200nm average particle diameter (D50)
＊ 10 bisphenol F-type acrylate resin, Nippon Kabushiki Kaisha
＊ 11 carboxyl group-containing resin having an amide imide structure manufactured by DIC
＊ 12 tricyclo [ 5.2.1.02, 6] decane dimethanol diacrylate, manufactured by Mizhongcun chemical industries, Ltd
＊ 13 Jer828 manufactured by Mitsubishi chemical corporation, bisphenol A epoxy resin, epoxy equivalent 189g/eq, liquid
＊ 14 Dicyclopentadiene type available from DIC corporation
＊ 15 Omnirad 369, manufactured by IGM Resins B.V., 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone
＊ 16 barium sulfate made by Sakai chemical industry Co., Ltd
[ Table 3]
As is clear from the results shown in the table, according to the present invention, a dry film was obtained in which the resin did not adhere to the knife and the sharpness did not deteriorate even when the dicing process was continuously performed, and as a result, the resin did not break, float, and the protective film did not float at the end portion.
Claims (6)
1. A dry film comprising a carrier film, a resin layer and a protective film,
the peel strength of the protective film to the resin layer is 0.010kgf/cm or more, and the peel strength of the protective film to the resin layer is greater than the peel strength of the carrier film to the resin layer.
2. The dry film according to claim 1, wherein a peel strength of the protective film to the resin layer is greater than a peel strength of the carrier film to the resin layer by 0.005kgf/cm or more.
3. The dry film according to claim 1, wherein the thickness is 60 μm or more.
4. The dry film according to claim 1, wherein said protective film has adhesiveness.
5. A cured product obtained by curing the resin layer of the dry film according to any one of claims 1 to 4.
6. An electronic component comprising the cured product according to claim 5.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112099312A (en) * | 2020-10-19 | 2020-12-18 | 河源诚展科技有限公司 | Photoresist dry film and preparation method thereof |
| CN112782936A (en) * | 2021-02-04 | 2021-05-11 | 杭州福斯特应用材料股份有限公司 | Photosensitive film and preparation method thereof |
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| US20030232165A1 (en) * | 2002-06-12 | 2003-12-18 | Katsuhiko Sumita | Surface protective film for adhesive resin and process for producing the same |
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| JP2016188924A (en) * | 2015-03-30 | 2016-11-04 | 日立化成株式会社 | Dry film, cured product, semiconductor device and method for forming resist pattern |
| JP2017052952A (en) * | 2016-09-20 | 2017-03-16 | 味の素株式会社 | Adhesive sheet with protective film, manufacturing method of laminate and manufacturing method of printed wiring board |
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| JP2002372781A (en) * | 2002-05-30 | 2002-12-26 | Hitachi Chem Co Ltd | Photosensitive element |
| JP5624184B1 (en) | 2013-06-28 | 2014-11-12 | 太陽インキ製造株式会社 | Dry film and printed wiring board |
| JP5882510B2 (en) * | 2014-06-30 | 2016-03-09 | 太陽インキ製造株式会社 | Photosensitive dry film and method for producing printed wiring board using the same |
| WO2017122460A1 (en) * | 2016-01-13 | 2017-07-20 | 太陽インキ製造株式会社 | Dry film and printed wiring board |
| JP2018125378A (en) * | 2017-01-31 | 2018-08-09 | 太陽インキ製造株式会社 | Dry film, cured product, printed wiring board, and method for manufacturing cured product |
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| JP2003140333A (en) * | 2001-11-01 | 2003-05-14 | Kanegafuchi Chem Ind Co Ltd | Photosensitive cover lay film excellent in peeling workability |
| US20030232165A1 (en) * | 2002-06-12 | 2003-12-18 | Katsuhiko Sumita | Surface protective film for adhesive resin and process for producing the same |
| CN102549499A (en) * | 2009-09-30 | 2012-07-04 | 可隆工业株式会社 | Dry film photoresist |
| JP2016188924A (en) * | 2015-03-30 | 2016-11-04 | 日立化成株式会社 | Dry film, cured product, semiconductor device and method for forming resist pattern |
| JP2017052952A (en) * | 2016-09-20 | 2017-03-16 | 味の素株式会社 | Adhesive sheet with protective film, manufacturing method of laminate and manufacturing method of printed wiring board |
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| CN112099312A (en) * | 2020-10-19 | 2020-12-18 | 河源诚展科技有限公司 | Photoresist dry film and preparation method thereof |
| CN112782936A (en) * | 2021-02-04 | 2021-05-11 | 杭州福斯特应用材料股份有限公司 | Photosensitive film and preparation method thereof |
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| JP2023057084A (en) | 2023-04-20 |
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| JP2020121481A (en) | 2020-08-13 |
| TWI747040B (en) | 2021-11-21 |
| TW202030238A (en) | 2020-08-16 |
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| JP7221064B2 (en) | 2023-02-13 |
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