CN207081941U - photosensitive dry film - Google Patents
photosensitive dry film Download PDFInfo
- Publication number
- CN207081941U CN207081941U CN201720798783.1U CN201720798783U CN207081941U CN 207081941 U CN207081941 U CN 207081941U CN 201720798783 U CN201720798783 U CN 201720798783U CN 207081941 U CN207081941 U CN 207081941U
- Authority
- CN
- China
- Prior art keywords
- photosensitive type
- dry film
- supporting base
- base material
- photosensitive
- 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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- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- FOUPWPPOMJVLGH-UHFFFAOYSA-N C(C=C)(=O)O.CC(C(=O)O)(CO)C Chemical compound C(C=C)(=O)O.CC(C(=O)O)(CO)C FOUPWPPOMJVLGH-UHFFFAOYSA-N 0.000 description 1
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- 241001232787 Epiphragma Species 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- NXQNMWHBACKBIG-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCC(O)(O)O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCC(O)(O)O NXQNMWHBACKBIG-UHFFFAOYSA-N 0.000 description 1
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- JNAHSTZIPLLKBQ-UHFFFAOYSA-N [O].CC=C Chemical compound [O].CC=C JNAHSTZIPLLKBQ-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
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- 150000002012 dioxanes Chemical class 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- PYHXGXCGESYPCW-UHFFFAOYSA-N diphenylacetic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-N 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
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- 238000002386 leaching Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
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- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
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Classifications
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The utility model provides a photosensitive dry film. The photosensitive dry film comprises a supporting substrate and a photosensitive resin layer positioned on the supporting substrate, wherein the supporting substrate comprises a first surface in contact with the photosensitive resin layer and a second surface opposite to the first surface, and the first surface has a non-smooth structure.
Description
Technical field
It the utility model is related to a kind of dry film, more particularly to a kind of supporting base material included with non-smooth structure and sense
The photosensitive type dry film of light type resin bed.
Background technology
Flexible printed wiring board is widely used in various 3C commodity, optical lens module, LCD module, solar cell etc.
Product.The production of traditional flexible printed wiring board is mainly using protecting glue material and liquid two kinds of materials of anti-welding green paint to provide electricity
The circuit protection film (coverlay) of road plate surface, to protect the copper circuit on soft board surface and increase circuit ability resistant to bending.
However, traditional protection glue material and the anti-welding green paint of liquid are above respectively present the defects of analyticity is low and pliability is poor because of in application,
Generally need to arrange in pairs or groups the two simultaneously use, so that the procedure for producing of flexible printed wiring board complicates.Therefore, it is at present to make more
Analyticity and flexible photosensitive type development cover layer (photoimageable can be had concurrently with trickle patterns of openings can be formed
Coverlay, PIC) carry out the circuit protection of flexible printed wiring board.
Modification acrylate or polyimides (polyimide, PI) are common photosensitive type development covering membrane material, and it can
Meet demand of the flexible circuit board for mechanical strength, pliability, resistance to dissolubility, dielectric property and heat resistance etc..However, change
Property acrylate cures after the diaphragm that is formed be clear, colorless, the diaphragm formed after polyimide curing is then to be transparent
Yellowish, when above-mentioned material is covered on flexible circuit board, the circuit diagram being arranged on flexible circuit board still can be observed
Case.In addition, said protection film has the high characteristic of glossiness, it is still to be improved in terms of cloudy surface with aesthetic feeling.
The content of the invention
In view of above technical problem, the utility model aims to provide a kind of photosensitive type dry film, and it is for forming resolution ratio
(Image resolution) excellent and low glossiness cover layer, can be provided for the circuit on flexible printed wiring board protection and
Peep-proof function, and have aesthetic feeling concurrently.
Therefore, the utility model first purpose is to provide a kind of photosensitive type dry film, and it includes supporting base material and positioned at this
Photosensitive type resin bed in supporting base material, the wherein supporting base material include the first surface that is contacted with the photosensitive type resin bed and with
The relative second surface of the first surface, and the first surface has non-smooth structure.
In section Example of the present utility model, the first surface of the supporting base material is surveyed with ASTM D523 standard methods
The glossiness obtained is less than 15GU.
In section Example of the present utility model, the mean roughness (Ra) of the first surface is thick compared with the second surface
Rugosity is high 110 nanometers to 850 nanometers.
In section Example of the present utility model, the first surface has 260 nanometers to 1000 nanometers of average roughness
Spend (Ra), the centerline average surface that usable 3D roughmeters, interferometer or AFM measure surface to be measured is coarse
Degree.
In section Example of the present utility model, the thickness of the supporting base material is 10 microns to 250 microns.
In section Example of the present utility model, the supporting base material is polyester mesentery or polyolefin mesentery.
In section Example of the present utility model, the photosensitive type resin bed passes through on the first surface of the supporting base material
Dry a photosensitive type resin combination and formed, and the photosensitive type resin combination includes 15 weight % to 80 weight % high score
Sub- binder, 2 weight % to the 65 weight % photopolymerizable compound containing unsaturated group, 0.5 weight % are to 20 weight %'s
The solvent of light initiator and surplus.The polymer binder can be acrylic acid series binder or polyimides system binder, and
The unsaturated group of the photopolymerizable compound containing unsaturated group can be acrylate-based.
In section Example of the present utility model, the photosensitive type resin combination also includes additive.
Another object of the present utility model is to provide a kind of method for forming photosensitive type development cover layer, comprising：
By photosensitive type dry film stacking as previously described on a substrate, formation one is sequentially comprising the substrate, the photosensitive type
The lamination structure of resin bed and the supporting base material；
At least a portion of the photosensitive type resin bed is exposed, and the branch support group is removed before or after the step of exposure
Material；And
Carry out development step,
Wherein the unexposed part of photosensitive type resin bed removes in the development step, and the photosensitive type resin bed is through exposing
The part of light forms photosensitive type development cover layer.
Above-mentioned photosensitive type development cover layer has cloudy surface characteristic and peep-proof function.
It is hereafter specific with part to enable above-mentioned purpose, technical characteristic and advantage of the present utility model to become apparent
Embodiment is described in detail.
Brief description of the drawings
Fig. 1 is the schematic diagram of one embodiment of the utility model photosensitive type dry film；
Fig. 2 is the schematic flow sheet that photosensitive type development cover layer is prepared using the utility model photosensitive type dry film；
Wherein, 1, release layer；2nd, photosensitive type resin bed；4th, supporting base material；5th, substrate.
Embodiment
The utility model photosensitive type dry film includes supporting base material and the photosensitive type resin bed in the supporting base material, one
Technical characterstic is that the supporting base material has non-smooth structure with the surface that the photosensitive type resin bed contacts.Have compared to use
The dry film of the supporting base material of smooth structure, the utility model photosensitive type dry film can provide that resolution ratio is more excellent and glossiness is low
Protection covered film structure, in addition to providing protection against, it may also provide the black aesthetic feeling of mist and cover the effect of circuit.
Fig. 1 is the schematic diagram of one embodiment of the utility model photosensitive type dry film.In the present embodiment, photosensitive type dry film
Photosensitive type resin bed 2 comprising supporting base material 4 and in supporting base material 4, supporting base material 4 contact with photosensitive type resin bed 2
Face is first surface, and the face relative with first surface is second surface, and first surface has non-smooth structure.In addition, in this reality
Apply in example, photosensitive type dry film also includes a release layer 1, positioned at the surface that photosensitive type resin bed 2 is not in contact with supporting base material 4
On, to provide the function of protecting and completely cut off photosensitive type resin bed 2 during the storage of photosensitive type dry film.This can be used in release layer 1
Separated type material known to utility model art, as long as photosensitive after required defencive function can be provided and removed
The surface of type resin bed 2 will not leave cull.The use of such release layer is the utility model art with logical
Normal skill sees to be based on after this case description the usual knowledge of its possessed and complete winner, and non-of the present utility model
Where technology emphasis, it will not go into details herein.
The surface (first surface) that the supporting base material of the utility model photosensitive type dry film contacts with photosensitive type resin bed has
Rough structure.
To produce atomized surface effect, above-mentioned first surface has the characteristic of low gloss.In some embodiments, supporting base material
First surface has the glossiness less than 15GU, such as low 14GU, 13GU, 12GU or lower glossiness, and preferably has
There is the glossiness less than 10GU, above glossiness is measured according to ASTM D523 standard methods.
To allow photosensitive type dry film that there is atomized surface effect and maintaining good photonasty, the supporting base material of the photosensitive type dry film
The roughness of first surface need to be high compared with the roughness of second surface, namely second surface is more flat compared to for first surface
Sliding, in terms of surface roughness (Ra), 110 nanometers to 850 high compared with the roughness of second surface of the roughness of preferable first surface is received
Rice.
In some embodiments, the second surface smooth structure of supporting base material is thick with 10 nanometers to 200 nanometers of surface
Rugosity (Ra), preferably have 100 nanometers to 170 nanometers of surface roughness.
In some embodiments, the first surface of the supporting base material of the photosensitive type dry film has 260 nanometers to 1000 nanometers
Surface roughness (Ra), preferably have 280 nanometers to 800 nanometers of surface roughness, for example, 300 nanometers, 350 nanometers, 400
Nanometer, 450 nanometers, 500 nanometers, 550 nanometers, 600 nanometers, 650 nanometers, 700 nanometers, 750 nanometers or higher of rough surface
Degree.If the surface roughness of first surface is too low, such as less than 260 nanometers, by because the glossiness too Gao Erying of first surface
Ring that the utility model photosensitive type dry film is exposed and development step after the cloudy surface texture of cover layer that is formed；If first surface
Surface roughness is too high, such as higher than 1000 nanometers, will negatively affect that the utility model photosensitive type dry film is exposed and development
The resolution ratio of the covering film figure formed after step.
In order that the covering that the photosensitive type resin bed of the photosensitive type dry film is formed after follow-up exposed and development step
Film figure has high-resolution, it is preferred that the single surface of supporting base material has non-smooth structure, preferably first surface, more
Goodly, the roughness of the first surface of supporting base material is high compared with the roughness of second surface 130 nanometers to 650 nanometers, such as high by 150
Nanometer, 200 nanometers, 300 nanometers, 400 nanometers, 500 nanometers or higher.
The species of the supporting base material of the photosensitive type dry film has no specifically limited, and the affiliated technology of any the utility model can be used
Base material known to field, it is preferred that use transparent supporting base material.For example, polyester mesentery or polyolefin can be used
Film is as supporting base material.The polyester mesentery is, for example, PET (PET) film, and polyolefin mesentery is, for example, poly-
Propylene film.In addition, the thickness of supporting base material is also without specifically limited, as long as required support performance can be provided, it is general and
Speech, the thickness of supporting base material can be 10 microns to 250 microns, preferably 12 microns to 50 microns, for example, 12 microns, 15 microns,
16 microns, 20 microns, 25 microns, 30 microns, 35 microns, 40 microns or 45 microns, but the utility model is not limited.
The photosensitive type resin bed of the utility model photosensitive type dry film on the first surface of the supporting base material by being coated with simultaneously
Dry photosensitive type resin combination and formed, above-mentioned photosensitive type resin combination, it can be used for printed circuit board (PCB) alkali etching, plating
Gold, change the processing procedures such as nickel leaching golden (electroless nickel immersion gold, ENIG), with photosensitive type resin combination
Gross weight meter, the photosensitive type resin combination includes 15 weight % to 80 weight % polymer binder, 2 weight % extremely
65 weight % photopolymerizable compound containing unsaturated group and 0.5 weight % to 20 weight % light initiator.The coating
Such as can be by using roll coater, chipping wheel coater (comma coater), gravure coater (gravure coater), gas
The well-known process such as knife coating machine, die coating machine, bar coater are carried out.The drying for example can dry 5 points with 70 DEG C to 150 DEG C of temperature
Clock was to 30 minutes or so.The photosensitive type resin combination can be the sense of any known circuit protection available for printed circuit board (PCB)
Light type protects glue material.In general, photosensitive type resin combination includes polymer binder, the photopolymerizable containing unsaturated group
The main components such as compound, light initiator, solvent.
Include, but are not limited to propylene available for polymer binder of the present utility model (polymeric binder) example
Acid resin, styrene resin, epoxy resin, amide resin, amideepoxy resin, polyimides predecessor, alkyd resin, phenolic aldehyde
Resin, polyurethane resin, the Epocryl obtained by the reaction of epoxy resin and (methyl) acrylic acid, by epoxy third
The sour modified epoxy acrylic ester resin and foregoing two or more mixing that the reaction of alkene acid ester resin and acid anhydrides obtains
Thing.
Photopolymerizable compound (photopolymerizable compound) one of the present utility model containing unsaturated group
As be monomer or short chain oligomer, it has ethylene type unsaturation functional group, includes monofunctional, difunctionality base or multifunctional
Base, above-mentioned ethylene type unsaturation functional group is acrylate-based, available for the photopolymerizable of the present utility model containing unsaturated group
The compound example includes, but are not limited to BDO two (methyl) acrylate (Isosorbide-5-Nitrae-butanediol di (meth)
Acrylate), 1,6-HD two (methyl) acrylate (1,6-hexanediol di (meth) acrylate), neopentyl
Ethylene glycol two (methyl) acrylate (neopentylglycol di (meth) acrylate), polyethylene glycol two (methyl) propylene
Acid esters (polyethyleneglycol di (meth) acrylate), neopentyl ethylene glycol two (methyl) acrylate adipic acid
Ester (neopentylglycol dipate di (meth) acrylate), neopentyl ethyleneglycol dimethacrylate hydroxyl spy penta
Acid esters (neopentylglycol di (meth) acrylate hydroxypivalate), the ring penta 2 of two (methyl) acrylic acid two
Alkene ester (dicyclopentdienyl di (meth) acrylate), two (methyl) acrylic acid bicyclopentadiene of caprolactone modification
Ester (caprolactone modified dicyclopentdienyl di (meth) acrylate), two (first of allylation
Base) cyclohexyl acrylate (allylated cyclohexyl di (meth) acrylate), two (methyl) acrylic acid isocyanuric acids
Ester (isocyanurate di (meth) acrylate), trimethylolpropane tris (methyl) acrylate (trimethylol
Propane tri (meth) acrylate), two pentaerythrityl three (methyl) acrylate (dipentaerythriol tri
(meth) acrylate), pentaerythrityl three (methyl) acrylate, trimethyl three (methyl) methyl acrylate, three (propylene oxygen second
Base) isocyanide uraturia ester (tris (acryloxyethyl) isocyanurate), two pentaerythrityl five (methyl) acrylate, two
Pentaerythrityl six (methyl) acrylate, trihydroxymethyl propane triacrylate, the glycerol propoxylate 3 third of ethyoxyl modification
Olefin(e) acid ester (propoxylate glycerol triacrylate), Ethoxylated bisphenol A dimethylacrylates
(bisphenol A ethoxylate dimethacrylate), aliphatic amine carbamate oligomer and foregoing two kinds or
A variety of mixtures.
In section Example of the present utility model, the polymer binder uses acrylic acid series binder (acrylic
Based binder) (such as acrylic resin) or polyimides system binder (polyimide based binder) (such as
Polyimides predecessor) and the photopolymerizable compound for containing unsaturated group be containing acrylate-based photopolymerizable compound.
Available for smooth initiator of the present utility model, it can provide free radical (free radical) after light irradiation, thoroughly
Cross the transmission of free radical, initiated polymerization.The species of light initiator has known to usually intellectual for this technical field,
Example includes, but are not limited to diphenylhydroxyethanone (benzoin), benzoin alkyl ether (benzoin alkyl ether), two
Phenylglyoxal (benzyl), ketal (ketals), acetophenone compound (acetophenones), benzophenone
(benzophenone), 9- phenylacridines (9-phenylacridine), 4,4- dimethyl-amines base-benzophenone (4,4-
Dimethyl-amino-benzophenone xanthone compound (thioxanthones), horse forint-acetonation), are vulcanized
Compound (morpholono-propanone), alpha-alcohol ketone, n- phenyl Gly, imidazoles dimer and foregoing two kinds are more
The mixture of kind.In addition, appropriate 9- phenylacridine homologues, such as (its content is hereby simultaneously in U.S. Patent No. 5,217,845
Enter herein by reference) disclosed in, it is also applied for being used as light initiator in the utility model.
Optionally, photosensitive type resin combination of the present utility model can include solvent, available for solvent of the present utility model
Include, but are not limited to methanol, second including any not atent solvent with the reaction of photosensitive type resin combination other components, the example
Alcohol, propyl alcohol, butanol, acetone, butanone, N- methyl 2- pyrrolones, methyl ethyl ketone, methyl cellosolve (methyl
Cellosolve), ethyl cellosolve (ethyl cellosolve), butyl cellosolve, toluene, N, N '-dimethyl formamide, third
Glycol monomethyl ether dimethyl sulfoxide (DMSO), diethyl sulfoxide, phenol, orthoresol, metacresol, paracresol, xylenols, halogenated phenol,
Catechol, tetrahydrofuran, dioxanes, dioxolanes, ring propylene glycol monomethyl ether, tetraethyleneglycol dimethyl ether, gamma-butyrolacton, pregnancy
Base mebenil, propylene glycol methyl ether acetate and foregoing two or more mixtures.
In section Example of the present utility model, with the gross weight meter of photosensitive type resin combination, polymer binder
Content can be 15 weight % to 50 weight %, the content of the photopolymerizable compound containing unsaturated group can be 2 weight % to 30
Weight %, the content of light initiator can be 0.5 weight % to 5 weight %, and surplus is solvent.In addition, photosensitive type resin group
Optionally it can be known to be used in preparing comprising other the utility model those of ordinary skill in the art into thing photosensitive
The additive of type dry film, the example of additive include but is not limited to filler (such as carbon black, silica, aluminum oxide), heat cure
Agent, dyestuff, levelling agent, defoamer and fire retardant.The content of above-mentioned additive can be by having in the utility model art
Usually intellectual adjusts to obtain through normal experiment.In some embodiments, carbon black is added in photosensitive type resin combination, with
Obtained photosensitive type is developed cover layer with more preferably matte black (matte black) effect, be visually that cloudy surface is black
Color, it is not easy to fingerprint is stained with, appearance tactile impression is good, and with more preferably peep-proof effect.About the specific of photosensitive type resin combination
Preparation method will illustrate in rear attached embodiment.
Photosensitive type dry film of the present utility model can be used for the cover layer that protection circuit is formed in printed circuit board surface.Cause
This, the utility model separately provides a kind of method for forming photosensitive type development cover layer, comprising：By above-mentioned photosensitive type dry film stacking
In on substrate, formation one sequentially includes the lamination structure of the substrate, the photosensitive type resin bed and the supporting base material；Expose the sense
At least a portion of light type resin bed, and the supporting base material is removed before or after the step of exposure；And carry out development step
Suddenly, wherein the unexposed part of photosensitive type resin bed removes in the development step, and the photosensitive type resin bed is exposed
Part forms photosensitive type development cover layer.
The glossiness that above-mentioned photosensitive type development cover layer is measured with ASTM D523 standard methods is less than 15GU.
Illustrate this method exemplified by using the photosensitive type dry film shown in Fig. 1 below.Fig. 2 is to use the utility model photosensitive type
Dry film prepares the schematic flow sheet of photosensitive type development cover layer.As shown in Fig. 2 the utility model forms photosensitive type development cover layer
Method be included in remove protection release layer 1 after, by the stacking of photosensitive type dry film on a substrate 5 so that photosensitive type resin
The one side that layer 2 does not contact with supporting base material 4 is conformed on the substrate 5 of photosensitive type development cover layer to be applied, and formation sequentially includes
The lamination structure of substrate 5, photosensitive type resin bed 2 and supporting base material 4.Then step is exposed, it is photosensitive according to what is formed
Type development covering film figure, expose at least a portion of the photosensitive type resin bed.In the situation that supporting base material 4 is transparent base
Under, supporting base material 4 can remove before or after the step of exposure, supporting base material 4 be removed preferably after step of exposure, with true
Protect the low gloss characteristic of formed cover layer.It is to be exposed to complete and after removing supporting base material 4, development step is carried out, to remove
2 unexposed part of photosensitive type resin bed, the exposed part of photosensitive type resin bed 2 form photosensitive type development cover layer.
The cover layer formed using the utility model photosensitive type dry film has excellent resolution ratio (90 microns or lower),
Simultaneously with more the texture that cloudy surface is dim, therefore, function not only attractive in appearance but also that circuit peep-proof can be provided in outward appearance (profile).
The utility model is further hereby illustrated with specific examples below, wherein, used measuring instrument and side
Method difference is as follows：
[glossiness test]
Utilize Grossmeters (model：VG2000；Nippon Denshoku companies), measured in ASTM D523 methods to be measured
The numerical value that 60 ° of sample Gloss.
[surface roughness test]
Use hand-held roughmeter (model：SURTRONIC S100 series), it is 100 microns × 100 micro- in measurement range
Under conditions of rice, the surface roughness (Ra) of testing sample is measured.
[resolution test]
It is exposed with exposing lattice number as 6 exposure energy, and spray development, after development treatment, use optics
Photosensitive type resin layer pattern after micro- sem observation solidification, to evaluate resolution ratio, dot pattern is open without residue minimum
Aperture (micron) is used as minimum resolution.
[examination of mist black substance sensing]
The covering film outward appearance that photosensitive type resin bed after being solidified with naked-eye observation is formed, if cloudy surface is presented in covering film outward appearance
And can not observe that cover layer underlying circuit designs, then it is evaluated as " 〇 "；Covered if covering film outward appearance is presented bright face and can observe
Epiphragma underlying circuit designs, then is evaluated as " X ".
Embodiment
<The preparation of photosensitive type resin combination 1>
Ratio mixing polymer binder shown in table 1 below, the photopolymerizable compound containing unsaturated group, light starting
Agent, thermal curing agents, solvent and inorganic filler, photosensitive type resin combination 1 is made after stirring.
Table 1
<The preparation of photosensitive type resin combination 2>
(1) preparation of polymer binder
First, polyamic acid oligomer is prepared as follows.By the pyromellitic acid dianhydride of 21.81 g (0.1 mole)
(pyromellitic dianhydride, PMDA) is dissolved in 126 g of N- methyl 2- pyrrolones (N-methyl-2-
Pyrrolidinone, NMP) in, heating gained mixture reacts two hours to 50 DEG C and under stirring state.Then slowly drip
Enter the 2- hydroxyethylacrylates (2-hydroxyethyl acrylate, HEA) of 2.322 g (0.02 mole), and keep temperature
Degree reacts two hours at 50 DEG C under stirring state.Thereafter, by the amido hexichol of 4,4'- bis- of 18.018 g (0.09 mole)
In mixture obtained by ether (4,4'-diamino-diphenyl ether, ODA) added to reaction, until completely dissolved, Yu Chi
Reacted six hours under 50 DEG C of temperature and stirring state, polyamic acid oligomer is made.
Then diamines monomer is prepared as follows.By the p-phenylenediamine (p- of 10.814 g (0.1 mole)
Phenylenediamine, pPDA) add in toluene solvant, it is slowly added under agitation 42.006 g (0.2 moles)
Trifluoro-acetic anhydride (trifluoroacetic acid anhydride, TFAA), in hold temperature 50 DEG C and stirring state under react
One hour, diamines monomer is made.
The 200 g polyamic acid oligomer (solid content 25%) is uniformly mixed with the 3 g diamines monomer,
Polymer binder is made.
(2) preparation of photosensitive type resin combination 2
Ratio mixing polymer binder shown in table 2 below, the photopolymerizable compound containing unsaturated group, light starting
Agent, solvent, inorganic filler and additive, photosensitive type resin combination 2 is made after stirring.
Table 2
<The preparation of photosensitive type resin combination 3>
Ratio mixing polymer binder shown in table 3 below, the photopolymerizable compound containing unsaturated group, light starting
Agent, thermal curing agents, solvent, inorganic filler and additive, photosensitive type resin combination 3 is made after stirring.
Table 3
<The preparation of photosensitive type dry film>
<Embodiment 1>
Photosensitive type resin combination 1 is spread evenly across with glossiness as shown in table 4, surface roughness and thickness
The first surface of the PET supporting base materials of property, and the photosensitive type tree that will be coated with 90 DEG C using hot wind convection type drying machine
Fat composition is dried about 5 minutes, to form the photosensitive type resin bed of 40 microns of thickness.Then photosensitive type resin bed not with the branch
On the surface of support group material contact, the PET film once the modification of poly- siloxy surface is bonded as diaphragm, being made has as shown in Figure 1
Structure photosensitive type dry film 1.
<Embodiment 2>
Photosensitive type dry film 2 is prepared in the same manner as example 1, and only using has various luster degree and surface roughness
The PET supporting base materials of property, as shown in table 4.
<Embodiment 3>
Photosensitive type dry film 3 is prepared in the same manner as example 1, only forms sense using photosensitive type resin combination 2
Light type resin bed, and the PET supporting base materials with various luster degree, surface roughness and thickness properties are used, as shown in table 4.
<Embodiment 4>
Photosensitive type dry film 4 is prepared in a manner of same as Example 3, only using with various luster degree, surface roughness,
And the PET supporting base materials of thickness properties, as shown in table 4.
<Embodiment 5>
Photosensitive type dry film 5 is prepared in the same manner as example 1, only forms sense using photosensitive type resin combination 3
Light type resin bed, and the PET supporting base materials with various luster degree, surface roughness and thickness properties are used, as shown in table 4.
<Embodiment 6>
Photosensitive type dry film 6 is prepared in a manner of same as Example 5, only using with various luster degree, surface roughness,
And the PET supporting base materials of thickness properties, as shown in table 4.
<Embodiment 7>
Photosensitive type dry film 7 is prepared in a manner of same as Example 5, only using has various luster degree and surface roughness
The PET supporting base materials of property, as shown in table 4.
<Embodiment 8>
Photosensitive type dry film 8 is prepared in a manner of same as Example 5, only using with various luster degree, surface roughness,
And the PET supporting base materials of thickness properties, as shown in table 4.
<Embodiment 9>
Photosensitive type dry film 9 is prepared in a manner of same as Example 5, only using with various luster degree, surface roughness,
And the PET supporting base materials of thickness properties, as shown in table 4.
<Comparative example 1 and comparative example 2>
Prepare in the same manner as example 1 and compare photosensitive type dry film 1 and compare photosensitive type dry film 2, only use respectively
PET supporting base materials with various luster degree and surface roughness property, as shown in table 4.
<Comparative example 3 and comparative example 4>
Prepared in a manner of same as Example 3 and compare photosensitive type dry film 3 and compare photosensitive type dry film 4, only used respectively
PET supporting base materials with various luster degree, surface roughness and thickness properties, as shown in table 4.
<Comparative example 5>
Prepared in a manner of same as Example 5 and compare photosensitive type dry film 5, only using thick with various luster degree, surface
The PET supporting base materials of rugosity and thickness properties, as shown in table 4.
Table 4
<The preparation (one) of photosensitive type development cover layer>
Using roughening pretreatment fluid CZ-8100 (Mec Company Ltd.), to the copper foil laminates of printing distributing board
(trade name：MCL-E-679；Hitachi be melted into limited company) copper surface handled, after then being cleaned with pure water dry.
The copper foil laminates be as by thickness be 12 microns copper foil laminated on a glass epoxy substrate obtained from.
Respectively using photosensitive type dry film 1, photosensitive type dry film 2, photosensitive type dry film 5 to photosensitive type dry film 9, compare photosensitive type and do
Film 1, compare photosensitive type dry film 2 and compare photosensitive type dry film 5 in the copper foil surface shape through foregoing pretreated copper foil laminates
Into photosensitive type development cover layer.First, by photosensitive type dry film or compare the diaphragm of photosensitive type dry film and remove, then by photosensitive type tree
Lipid layer fits to copper foil surface together with supporting base material.Then pressing type vacuum pressing-combining machine (model is used：MVP-600；Changxing material
Limited company) pressing (compacting hot plate temperature：50 DEG C to 60 DEG C；It is evacuated the time：30 seconds；Vacuum pressure：It is less than
2hPa；Press time：30 seconds；And pressing pressure：0.5MPa to 0.7MPa), form one and include copper foil laminates, photosensitive type tree
The lamination structure of lipid layer and supporting base material.
After the lamination structure is placed into 0.5 hour at room temperature, it is exposed and develops, with the copper foil of copper foil laminates
Surface forms photosensitive type development cover layer.First, set 21 lattice to expose lattice several pieces (step tablet), use with high-pressure water
Direct imaging exposure device (model of the silver-colored lamp as light source：DXP-3512；ORC MANUFACTURING limited companies) enter
Row exposure.Place after exposure 30 minutes, then remove supporting base material at room temperature.Then 30 DEG C of 1% sodium carbonate is used
Solution carries out the spray development of 30 seconds to 50 seconds, and the unexposed part of photosensitive type resin bed is removed.By 21 lattice exposure lattice several pieces
Gloss remaining exposure lattice number as 9 to 10 sensitivity (unit of the exposure energy as photosensitive type resin bed；mJ/cm2).Finally
In baking oven (temperature：150 DEG C to 155 DEG C) in baking 50 minutes to 60 minutes, then develop cover layer to the photosensitive type that is formed
Pattern is evaluated, as a result as shown in table 5 below.
<The preparation (two) of photosensitive type development cover layer>
Concentration 5% is to 10%H2SO4The aqueous solution, to the copper foil laminates (trade name of printing distributing board：MCL-E-
679；Hitachi be melted into limited company) copper surface handled, after then being cleaned with pure water dry.The copper foil laminates are
As by thickness be 12 microns copper foil laminated on a pi substrate obtained from.
Respectively using photosensitive type dry film 3, photosensitive type dry film 4, compare photosensitive type dry film 3 and compare photosensitive type dry film 4 and passing through
The copper foil surface of foregoing pretreated copper foil laminates forms photosensitive type development cover layer.First, by photosensitive type dry film or ratio
Diaphragm compared with photosensitive type dry film is removed, then photosensitive type resin bed is fitted into copper foil surface together with supporting base material.Then use
Hot roller pressing machine presses (pressing-in temp：60 DEG C to 70 DEG C；Pressing speed：0.5M/min to 1.0M/min；Pressing pressure：
5kgf/cm2To 6kgf/cm2), form a lamination structure for including copper foil laminates, photosensitive type resin bed and supporting base material.
After the lamination structure is placed into more than 30 minutes at room temperature, it is exposed and develops, with copper foil laminates
Copper foil surface forms photosensitive type development cover layer.First, set 21 lattice expose lattice several pieces, and use using extra-high-pressure mercury vapour lamp as
The direct imaging exposure device of light source is exposed.Supporting base material is removed, and toasted 15 minutes at a temperature of 90 DEG C.Most
Afterwards, the spray development of 44 seconds is carried out by 30 DEG C of 1% wet chemical, the unexposed part of photosensitive type resin bed is gone
Remove.Using several pieces gloss remaining exposure lattice number of 21 lattice exposure lattice as 6 to 8 exposure energy as photosensitive type resin bed sensitivity
(unit；mJ/cm2).Finally in baking oven (temperature：170 DEG C to 275 DEG C) in baking 60 minutes to 120 minutes, then to being formed
Photosensitive type development covering film figure evaluated, it is as a result as shown in table 5 below.
Table 5
| Resolution ratio (micron) | Mist black substance sense | |
| Embodiment 1 | 90 | 〇 |
| Embodiment 2 | 80 | 〇 |
| Embodiment 3 | 70 | 〇 |
| Embodiment 4 | 70 | 〇 |
| Embodiment 5 | 70 | 〇 |
| Embodiment 6 | 70 | 〇 |
| Embodiment 7 | 60 | 〇 |
| Embodiment 8 | 70 | 〇 |
| Embodiment 9 | 80 | 〇 |
| Comparative example 1 | >100 | x |
| Comparative example 2 | 70 | x |
| Comparative example 3 | 70 | x |
| Comparative example 4 | >100 | 〇 |
| Comparative example 5 | >100 | 〇 |
As can be seen from the results of table 5, the cover layer that photosensitive type dry film of the present utility model is formed has excellent resolution ratio (90
Micron is lower), while have more good mist black substance sense, function not only attractive in appearance but also that circuit peep-proof can be provided.
From comparative example 1 and the result of embodiment 1 and 2, if the surface roughness of the first surface of supporting base material is too small
(being, for example, less than 260 nanometers), and the roughness system of the first surface of supporting base material is too small compared with the roughness discrepancy of second surface
(being, for example, less than 110 nanometers), obtained cover layer do not have good mist black substance sense, the pattern that photosensitive type resin bed is formed
Resolution ratio is also bad.From the result of comparative example 2, comparative example 3 and embodiment 1 to 4, if the table of the first surface of supporting base material
Surface roughness is too small (being, for example, less than 260 nanometers), and obtained cover layer does not have good mist black substance sense.
From comparative example 4 and the result of embodiment 3 and 4, if the roughness of the first surface of supporting base material and the second table
The roughness discrepancy in face is too small (being, for example, less than 110 nanometers), then the resolution ratio of obtained pattern is bad.
From comparative example 5 and the result of embodiment 5 to 9, if the surface roughness of the first surface of supporting base material is too big
(being greater than 1000 nanometers), and the roughness of the first surface of supporting base material is too big compared with the roughness discrepancy of second surface
(being greater than 850 nanometers), then the resolution ratio of obtained pattern is bad.
Above-described embodiment is only illustrative principle of the present utility model and its effect, and illustrates skill of the present utility model
Art feature, not for limitation protection category of the present utility model.It is any to be familiar with this technology person without prejudice to of the present utility model
Under technical principle and spirit, can unlabored change or arrangement, belong to the scope advocated of the utility model.Therefore, this reality
With new rights protection scope as listed by rear attached claim.
Claims (6)
1. a kind of photosensitive type dry film, it includes supporting base material and the photosensitive type resin bed in the supporting base material, the wherein branch
Support group material includes the first surface that is contacted with the photosensitive type resin bed and the second surface relative with the first surface, and this first
Surface has non-smooth structure.
2. photosensitive type dry film as claimed in claim 1, the wherein first surface of the supporting base material are with ASTM D523 standard methods
The glossiness measured is less than 15GU.
3. the mean roughness (Ra) of photosensitive type dry film as claimed in claim 1, the wherein first surface is compared with the second surface
Roughness it is high 110 nanometers to 850 nanometers.
4. photosensitive type dry film as claimed in claim 1, the wherein first surface are thick with 260 nanometers to 1000 nanometers be averaged
Rugosity (Ra).
5. photosensitive type dry film as claimed in claim 1, the wherein thickness of the supporting base material are 10 microns to 250 microns.
6. photosensitive type dry film as claimed in claim 1, the wherein supporting base material are polyester mesentery or polyolefin mesentery.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TWTW10201615 | 2017-01-26 | ||
| TW106201615U TWM543773U (en) | 2017-01-26 | 2017-01-26 | Photosensitive dry film |
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| Publication Number | Publication Date |
|---|---|
| CN207081941U true CN207081941U (en) | 2018-03-09 |
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ID=59689624
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201720798783.1U Active CN207081941U (en) | 2017-01-26 | 2017-07-04 | photosensitive dry film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3215657U (en) |
| KR (1) | KR200490675Y1 (en) |
| CN (1) | CN207081941U (en) |
| TW (1) | TWM543773U (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107329370A (en) * | 2017-01-26 | 2017-11-07 | 长兴材料工业股份有限公司 | Photosensitive dry film and application thereof |
| CN109541889A (en) * | 2018-12-19 | 2019-03-29 | 江苏艾森半导体材料股份有限公司 | Negative photoresist for semiconductor packaging process |
| CN113604164A (en) * | 2021-08-04 | 2021-11-05 | 苏州城邦达益材料科技有限公司 | FPC photosensitive cover film for MiniLED |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102214641B1 (en) * | 2018-07-16 | 2021-02-10 | 삼성전기주식회사 | Printed circuit board |
| US20220390844A1 (en) * | 2019-09-30 | 2022-12-08 | Taiyo Ink Mfg. Co., Ltd. | Cured coating film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4159094B2 (en) * | 2003-10-15 | 2008-10-01 | 東京応化工業株式会社 | Photosensitive resin composition and photosensitive dry film using the same |
| US9880467B2 (en) * | 2012-08-01 | 2018-01-30 | Lg Chem, Ltd. | Photo-curable and thermo-curable resin composition and dry film solder resist |
| KR101734425B1 (en) * | 2013-09-24 | 2017-05-11 | 주식회사 엘지화학 | Preparation method for dry film solder resist and film laminate used therein |
| KR20150047863A (en) * | 2013-10-25 | 2015-05-06 | 주식회사 엘지화학 | Photo-curable and thermo-curable resin composition, and dry film solder resist |
-
2017
- 2017-01-26 TW TW106201615U patent/TWM543773U/en unknown
- 2017-07-04 CN CN201720798783.1U patent/CN207081941U/en active Active
-
2018
- 2018-01-23 JP JP2018000215U patent/JP3215657U/en active Active
- 2018-01-26 KR KR2020180000402U patent/KR200490675Y1/en active IP Right Grant
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107329370A (en) * | 2017-01-26 | 2017-11-07 | 长兴材料工业股份有限公司 | Photosensitive dry film and application thereof |
| CN107329370B (en) * | 2017-01-26 | 2021-01-05 | 长兴材料工业股份有限公司 | Photosensitive dry film and application thereof |
| CN109541889A (en) * | 2018-12-19 | 2019-03-29 | 江苏艾森半导体材料股份有限公司 | Negative photoresist for semiconductor packaging process |
| WO2020125520A1 (en) * | 2018-12-19 | 2020-06-25 | 江苏艾森半导体材料股份有限公司 | Negative photoresist used for semiconductor encapsulation process |
| CN109541889B (en) * | 2018-12-19 | 2020-06-26 | 江苏艾森半导体材料股份有限公司 | Negative photoresist for semiconductor packaging process |
| US11644750B2 (en) | 2018-12-19 | 2023-05-09 | Jiangsu Aisen Semiconductor Material Co., Ltd. | Negative photoresist used for semiconductor encapsulation process |
| CN113604164A (en) * | 2021-08-04 | 2021-11-05 | 苏州城邦达益材料科技有限公司 | FPC photosensitive cover film for MiniLED |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3215657U (en) | 2018-04-05 |
| KR200490675Y1 (en) | 2019-12-16 |
| TWM543773U (en) | 2017-06-21 |
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