CN109541887A - The photocuring film of photosensitive polymer combination and printed circuit board with the photocuring film - Google Patents

The photocuring film of photosensitive polymer combination and printed circuit board with the photocuring film Download PDF

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Publication number
CN109541887A
CN109541887A CN201811105037.5A CN201811105037A CN109541887A CN 109541887 A CN109541887 A CN 109541887A CN 201811105037 A CN201811105037 A CN 201811105037A CN 109541887 A CN109541887 A CN 109541887A
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layer
acid
cured film
film
photosensitive polymer
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斋藤隆英
木村健人
土屋雅裕
柿内直也
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Tamura Corp
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Tamura Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The purpose of the present invention is to provide the photocuring film of photosensitive polymer combination and with the printed circuit board of the photocuring film, insulating reliability in the flexibility and insulating reliability, particularly thickness direction of the photocuring film is excellent and surface element is roughened, so that glossiness be made to reduce.The cured film is the cured film for covering printed circuit board, photosensitive polymer combination, the second layer that the cured film has the first layer of the printed circuit board side and is arranged on the surface of the first layer, the film thickness of the first layer is more than 2.0 μm and does not contain (E) delustering agent, and the second layer contains (E) delustering agent.

Description

The photocuring film of photosensitive polymer combination and with the photocuring film printing electricity Road plate
Technical field
The present invention relates to implementing the surface after delustring and flexibility and photosensitive with excellent insulating reliability The photocuring film of property resin combination and printed circuit board with the photocuring film.
Background technique
Printed circuit board is the pattern in order to form conductor circuit on substrate, and is equipped on electronic component by welding The pad of the pattern and use, the loop feature other than the solder pad is covered by the insulating coating as photocuring film sometimes Lid.It as a result, when electronic component is welded in printed circuit board, prevents solder attachment in unnecessary portion, and prevents electricity Road conductor is directly exposed to air, is corroded because of oxidation, humidity.
In addition, considering for insulating coating from covering power etc., sometimes requires that and roughening (delustring) is implemented to its surface And weaken gloss.In order to which roughening is implemented on the surface to insulating coating, cooperate filler in photosensitive polymer combination sometimes.Separately On the one hand, in recent years, make the insulating coating such as the conductive component and solder resist film that function as electro-magnetic screen layer sometimes Contact, even if in this case, also requiring exhausted on the thickness direction of excellent insulating reliability, particularly insulating coating The insulating coating of edge reliability.
However, and if cooperating filler in photosensitive polymer combination in order to which roughening is implemented on the surface to insulating coating, Sufficient insulating reliability can not be then obtained on the thickness direction of insulating coating sometimes, the insulating coating after implementing delustring In, there is room for improvement about the insulating reliability on thickness direction.
In addition, since the miniaturization of electronic equipment, complication of internal structure etc. continue to develop, flexibility is printed Printed circuit board requires excellent flexibility.Therefore, other than metal pad part, for the exhausted of covering flexible printed circuit board Edge overlay film requires excellent flexibility.
In order to provide flexibility excellent insulating coating, following composition is proposed, the composition contains (A) in 1 molecule Photonasty prepolymer, (B) Photoepolymerizationinitiater initiater, (C) diluent with 2 or more unsaturated double-bonds and 1 or more carboxyl, (D) polybutadiene and (F) polyurethane particulate of epoxide, (E) with 1 or more internal epoxy group in 1 molecule (patent document 1).
However, the miniaturization of current electronic device further develops, the photocuring film obtained by the composition of patent document 1 Flexibility and insufficient, in addition, the insulating reliability when contacting conductive component on insulation-coated, on thickness direction It cannot say sufficiently.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2002-293882 bulletin
Summary of the invention
Subject to be solved by the invention
In view of said circumstances, the purpose of the present invention is to provide in flexibility and insulating reliability, particularly thickness direction Insulating reliability is excellent and surface element is carried out roughening and the cured film that reduces glossiness and with the cured film Printed circuit board.
Means for solving the problems
The scheme of the invention is a kind of cured film, is printed circuit board, photosensitive polymer combination for covering Cured film, the cured film there is the first layer of the printed circuit board side and be arranged on the surface of the first layer the Two layers, the film thickness of the first layer is more than 2.0 μm and does not contain (E) delustering agent, and the second layer contains (E) delustering agent.
The scheme of the invention is a kind of cured film, wherein (E) delustering agent contains Polyurethane resin powder or silicon tree Cosmetics end.
The scheme of the invention is a kind of cured film, wherein relative to the photosensitive polymer combination for forming the second layer 100 mass parts of photoresist, containing it is more than 10 mass parts and 100 below the mass described in (E) delustering agent.
The scheme of the invention is a kind of cured film, wherein relative to the photosensitive polymer combination for forming the second layer 100 mass parts of photoresist, containing it is more than 30 mass parts and 80 below the mass described in (E) delustering agent.
The scheme of the invention is a kind of cured film, wherein 60 ° of gloss values for solidifying film surface are less than 70.
The scheme of the invention is a kind of cured film, wherein the film thickness of the second layer is 5.0 μm or more.
The scheme of the invention is a kind of cured film, is made of the first layer and the second layer.
The scheme of the invention is a kind of cured film, wherein the film thickness of the first layer and the second layer adds up to 10 μ M or more and 100 μm or less.
The scheme of the invention is a kind of cured film, wherein the first layer is to contain (A) photoresist, (B) photopolymerization The solidfied material of first photosensitive polymer combination of initiator, (C) (methyl) acrylate monomer and (D) epoxide, The second layer is to contain (A) photoresist, (B) Photoepolymerizationinitiater initiater, (C) (methyl) acrylate monomer, (D) epoxidation Close the solidfied material of second photosensitive polymer combination of object and (E) delustering agent.
The scheme of the invention is a kind of cured film, is photocuring film.
The scheme of the invention is the printed circuit board with above-mentioned cured film.
Invention effect
According to the solution of the present invention, cured film has the second layer positioned at the first layer of lower layer side and positioned at upper layer side, The film thickness of first layer is more than 2.0 μm and does not contain (E) delustering agent, and the second layer contains (E) delustering agent, so as to obtain softness Property and insulating reliability, particularly thickness direction on insulating reliability is excellent and surface element is carried out roughening and makes glossiness Reduced cured film.
According to the solution of the present invention, (E) delustering agent contains Polyurethane resin powder or silicone powders, so as into The flexibility of one step raising cured film.
According to the solution of the present invention, the photoresist relative to the photosensitive polymer combination for forming the second layer 100 mass parts, containing more than 10 mass parts and 100 (E) delustering agent below the mass, so as to more reliably be made The cured film that glossiness reduces.
According to the solution of the present invention, the film thickness of the second layer is 5.0 μm or more, more reliably makes glossiness so as to obtain Reduced cured film.
Specific embodiment
Next, being illustrated below to cured film of the invention.Cured film of the invention is for covering printed circuit Plate, photosensitive polymer combination cured film, the cured film include the first layer of the printed circuit board side；And it sets The second layer being placed on the surface of the first layer, the film thickness of the first layer are more than 2.0 μm and do not contain (E) delustering agent, institute It states the second layer and contains (E) delustering agent.
Cured film of the invention is formed as stepped construction, includes first layer, is located at printed circuit board side, i.e. lower layer Side；And the second layer, it is located at the position opposed with printed circuit board across first layer, i.e. upper layer side.The second layer becomes layer The surface layer of stack structure.First layer is the solidfied material of the first photosensitive polymer combination, and the second layer is and the first photoresist group Close the solidfied material of the second different photosensitive polymer combination of object.Above-mentioned stepped construction can be to be made of first layer and the second layer Stepped construction, other layers, example can also be formed between printed circuit board and first layer and/or between first layer and the second layer Such as other photosensitive polymer combinations different from the first photosensitive polymer combination and the second photosensitive polymer combination Solidfied material.
For being provided with the printed circuit board of cured film of the invention, for example, flexible printed circuit board.
Solidfied material, the i.e. first layer of the first photosensitive polymer combination without (E) delustering agent is that top is not carried out slightly Change and that insulating reliability on flexibility and insulating reliability, particularly thickness direction is excellent is coating.In addition, containing (E) Solidfied material, the i.e. second layer of second photosensitive polymer combination of delustering agent, is with flexibility and surface element is carried out roughening And it is coating to reduce glossiness.Therefore, cured film of the invention becomes the stacking knot with above-mentioned first layer and the second layer Structure, so being that insulating reliability on flexibility and insulating reliability, particularly thickness direction is excellent and surface element is carried out The cured film for being roughened and reducing glossiness.
First photosensitive polymer combination
As long as the ingredient of the first photosensitive polymer combination is free of (E) delustering agent, it is not particularly limited, such as contain (A) Photoresist, (B) Photoepolymerizationinitiater initiater, (C) (methyl) acrylate monomer and (D) epoxide.Below to first Each ingredient of photosensitive polymer combination is illustrated.
(A) photoresist
Photoresist is not particularly limited, for example, having containing for 1 or more photosensitive unsaturated double-bond Carboxyl photoresist.As the example of the photoresist containing carboxyl, the polyacid obtained in the following manner can be enumerated The free-radical polymerised unsaturated monocarboxylic epoxy resin of the modified by polyacid such as modified epoxy (methyl) acrylate: make propylene In the free-radical polymerised unsaturated monocarboxylics and 1 molecule such as acid, methacrylic acid (hereinafter sometimes referred to " (methyl) acrylic acid ") At least part of the epoxy group of multi-functional epoxy resin with 2 or more epoxy groups reacts, and obtains epoxy (first Base) the free-radical polymerised unsaturated monocarboxylic epoxy resin such as acrylate, further make polyacid or its acid anhydrides and life At hydroxyl reaction.
As long as epoxy resin more than 2 function of multi-functional epoxy resin, then can be used any epoxy resin. The epoxide equivalent of multi-functional epoxy resin is not particularly limited, but preferably 2000g/eq is hereinafter, more preferable 1000g/eq Hereinafter, particularly preferably 100g/eq~500g/eq.For multi-functional epoxy resin, for example, biphenyl type epoxy tree Rouge, biphenyl aralkyl-type epoxy resin, phenyl aralkyl-type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy tree The rubber modified epoxy resins such as rouge, modifying epoxy resin by organosilicon, 6-caprolactone modified epoxy, bisphenol A-type, bisphenol-f type, It is the cresol novolak type epoxy resins such as the phenol novolak type epoxy resins such as bisphenol-A D type, o-cresol phenolic varnish type, double Phenol A phenolic resin varnish type epoxy resin, annular aliphatic polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, contracting Water glycerol amine type polyfunctional epoxy resin, hetero ring type polyfunctional epoxy resin, bis-phenol modified novolac type epoxy resin, more officials Energy modified novolac type epoxy resin, phenols and condensation product type epoxy resin of the aromatic aldehyde with phenolic hydroxyl group etc..Separately Outside, it can also use and the halogen atoms such as Br, Cl are imported into the resulting product of these resins.It can be used alone above-mentioned asphalt mixtures modified by epoxy resin Rouge, the above-mentioned epoxy resin that can also be mixed with two or more.
Free-radical polymerised unsaturated monocarboxylic is not particularly limited, for example, acrylic acid, metering system Acid, crotonic acid, cinnamic acid etc., preferably acrylic acid, methacrylic acid.For epoxy resin and free-radical polymerised unsaturated single carboxylic The reaction method of acid is not particularly limited, such as can be by heating epoxy resin and free radical polymerization in diluent appropriate Property unsaturated monocarboxylic and make its reaction.
It is given birth to by polyacid, multi-anhydride with by the epoxy resin and reacting for free-radical polymerised unsaturated monocarboxylic At hydroxyl react, so that carboxyl that will be free imports resin.Polyacid or its acid anhydrides are not particularly limited, it can To use saturation, unsaturated polyacid or its acid anhydrides.As specific polyacid, for example, succinic acid, maleic acid, Adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3- methyl tetrahydrophthalic acid, 4- methyl tetrahydro neighbour benzene two Formic acid, 3- ethyl tetrahydrophthalic acid, 4- ethyl tetrahydrophthalic acid, hexahydrophthalic acid, 3- methyl hexahydro neighbour's benzene Dioctyl phthalate, 4- methylhexahydrophthaacid acid, 3- ethyl hexahydrophthalic acid, 4- ethyl hexahydrophthalic acid, methyl four Hydrogen phthalic acid, methylhexahydrophthaacid acid, methylene tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic tetrahydro neighbour benzene two Formic acid, trimellitic acid, Pyromellitic Acid and diglycolic acid etc. can enumerate above-mentioned polyacid as specific multi-anhydride Acid anhydrides.It can be used alone above compound, the above compound that can also be mixed with two or more.
The above-mentioned free-radical polymerised unsaturated monocarboxylic epoxy resin of modified by polyacid can also be used as photosensitive containing carboxyl Property resin use, but can according to need, make the glycidol with 1 or more free-radical polymerised unsaturated group and epoxy group The carboxyl of based compound and the free-radical polymerised unsaturated monocarboxylic epoxy resin of above-mentioned modified by polyacid reacts, thus Free-radical polymerised unsaturated group is further imported, to form the tree of photonasty containing carboxyl that photonasty is further improved Rouge.
The photoresist containing carboxyl that the photonasty is further improved is anti-by the glycidyl compound It answers, makes free-radical polymerised unsaturated group and the free-radical polymerised unsaturated monocarboxylic epoxy backbone of modified by polyacid Thus side chain bonding becomes the resin that photopolymerization reaction further increases and has excellent photobehavior.As with 1 The compound of above free-radical polymerised unsaturated group and epoxy group, is not particularly limited, for example, acrylic acid shrinks Glyceride, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether Deng.Furthermore, it is possible to have 1 glycidyl in 1 molecule, it is possible to have multiple glycidyls.It is above-mentioned have 1 with Upper free-radical polymerised unsaturated group and the compound of epoxy group can be used alone, and can also be mixed with two or more.
In addition, the sour modified amido formic acid obtained in the following manner can be used as photoresist containing carboxyl It is esterified free-radical polymerised unsaturated monocarboxylic epoxy resin: making dihydromethyl propionic acid etc. that there is the compound of hydroxyl and carboxyl And the polyisocyanate compounds such as hexamethylene diisocyanate and epoxy (methyl) acrylate etc. are free-radical polymerised not Saturation mono-carboxylic acid's epoxy resin reacts.
As photoresist containing carboxyl, for example, the substance obtained by following manner: making b) every 1 carboxylic At least one kind of fatty acid that the carbon atom number of base is 8 or more and c) free-radical polymerised unsaturated monocarboxylic and a) have in 1 molecule There is the epoxy group of the epoxy resin of 2 or more epoxy groups to react, changes thus to obtain the long chain fatty acids as reaction product Property contain the modified epoxy of ethylenic bond unsaturated group, further make d) multi-anhydride with by long chain fatty acids and/or from Hydroxyl (the predominantly secondary hydroxyl generated by the reaction of the epoxy group of the carboxyl and epoxy resin of base polymerism unsaturated monocarboxylic Base) addition, so that free carboxyl is imported above-mentioned resin.
A) with the epoxy resin of 2 or more epoxy groups in 1 molecule
As long as the epoxy resin more than 2 function of epoxy resin in 1 molecule with 2 or more epoxy groups, then can be used and appoint What epoxy resin.The epoxide equivalent of epoxy resin in 1 molecule with 2 or more epoxy groups is not particularly limited, from anti- Only photonasty and flexibility because caused by reducing the importing ratio of free-radical polymerised unsaturated monocarboxylic and long chain fatty acids From the viewpoint of reduction, preferably 2000g/eq hereinafter, more preferably 1000g/eq hereinafter, particularly preferably 100g/eq~500g/eq.
For having the epoxy resin of 2 or more epoxy groups in 1 molecule, for example, biphenyl aralkyl type epoxy tree It is rouge, phenyl aralkyl-type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene-type epoxy resin, organic The rubber modified epoxy resins such as silicon modified epoxy resin, 6-caprolactone modified epoxy, bisphenol A-type, bisphenol-f type, bisphenol-A D The cresol novolak type epoxy resins, ring-shaped fat such as the phenol novolak type epoxy resins such as type, o-cresol phenolic varnish type Race's polyfunctional epoxy resin, glycidyl ester type polyfunctional epoxy resin, glycidic amine type polyfunctional epoxy resin, hetero ring type Polyfunctional epoxy resin, bis-phenol modified novolac type epoxy resin, multifunctional modified novolac type epoxy resin, phenols and The condensation product type epoxy resin of aromatic aldehyde with phenolic hydroxyl group, is imported with adamantane bone at the epoxy resin containing fluorene skeleton The epoxy resin etc. of frame.Furthermore it is also possible to use the substance that the halogen atoms such as Br, Cl are imported above-mentioned resin and are formed.
Wherein, it is examined from the viewpoint of the sensitivity of photosensitive polymer combination, the flexibility of solidfied material and insulating reliability Consider, preferably phenyl aralkyl-type epoxy resin, dicyclopentadiene-type epoxy resin.
B) fatty acid that the carbon atom number of every 1 carboxyl is 8 or more
There are 2 or more epoxy groups in the fatty acid (long chain fatty acids) and 1 molecule that the carbon atom number of every 1 carboxyl is 8 or more Epoxy resin epoxy reaction, and the long-chain hydrocarbon structure from above-mentioned fatty acid is imported into the resin, thus improved photosensitive The flexibility (flexibility) and insulating reliability of the solidfied material of property resin combination.For every 1 carboxyl carbon atom number be 8 with On fatty acid be not particularly limited, saturation, unsaturated fatty acid can be used, further, it is possible to use straight-chain, branch-like Fatty acid.For above-mentioned fatty acid, for example, carbon atom number be 8 or more monoacid, carbon atom number be 16 or more Binary acid, from the aspect of flexibility and the balance of dry to touch, preferably above-mentioned monoacid and binary acid are straight-chain Or with 2 or less carbon atom numbers be 2 side chains below branch-like.
In addition, by long chain fatty acids structure import epoxy resin, and the different epoxy groups of above-mentioned epoxy resin via Fatty acid and be mutually bonded, thus, it is possible to be formed as using from long chain fatty acids the high long-chain hydrocarbon skeleton of flexibility and lead to Structure made of covalent bond is crosslinked skeleton more upright and outspoken possessed by epoxy resin is crossed, in turn, is helped from the structure From the aspect of the flexibility of cured coating film and solder heat resistance, preferred fatty acid contains at least one kind of binary acid.
More from long chain fatty acids, flexibility and the high long-chain hydrocarbon skeleton of insulating reliability by importing In the case where flexibility and insulating reliability that cured coating film can be further increased, pass through the carbon in addition to above-mentioned every 1 carboxyl Other than the binary acid that atomicity is 8 or more, the monoacid for being also while using the carbon atom number of every 1 carboxyl 8 or more, thus, it is possible to Enough composition ratios for improving the ingredient from long chain fatty acids, and moderately control fatty acid, polyfunctional epoxy resin with And the molecular weight of the reaction product of free-radical polymerised unsaturated monocarboxylic.By moderately controlling the molecule as described above Amount, being capable of dry to touch, alkali-developable and sensitivity balanced and that reliably improve the film after drying.In addition, passing through Monoacid and binary acid are used simultaneously, additionally it is possible to which being reliably conducive to insulating reliability, (insulation especially on thickness direction can By property) and solder heat resistance raising.
By more moderately controlling the molecular weight, so that above-mentioned each characteristic is more balancedly improved, from this viewpoint, The straight-chain that particularly preferably carbon atom number containing every 1 carboxyl is 18 or more is saturated monoacid.
From the aspect of assigning flexibility and insulating reliability to solidfied material, the carbon atom number of every 1 carboxyl be 8 with On, preferably 10 or more.On the other hand, the upper limit value of the carbon atom number of every 1 carboxyl is not particularly limited, it is good from maintenance From the aspect of good alkali-developable, preferably 24 hereinafter, particularly preferred 22 or less.
The specific example for the fatty acid that carbon atom number for every 1 carboxyl is 10 or more can be enumerated as monoacid Capric acid (C10), hendecanoic acid (C11), lauric acid (C12), tridecanoic acid (C13), myristic acid (C14), pentadecanoic acid (C15), palmitinic acid (hexadecanoic acid: C16), Heptadecanoic acide (C17), stearic acid (C18), isostearic acid (C18), tuberlostearic acid (C19), arachic acid (C20), behenic acid (C22), tricosanic acid (C23), lignoceric acid (C24), hexacosoic acid (C26), octocosoic acid (C28), melissic acid (C30) etc..
As binary acid, eicosane diacid (C20), ethyl octadecane diacid (C20), 20 carbon, two enedioic acid can be enumerated (C20), vinyl octadecene diacid (C20), 20 carbon of dimethyl, two enedioic acid (C22), dimethyl eicosane diacid (C22), diphenyl hexadecandioic acid (hexadecane diacid) (C28), the C36 generated by the Dimerized reaction of the unsaturated fatty acids such as oleic acid (C18) Dimeric dibasic acid, hydrogenation C36 dimeric dibasic acid characterized by the olefinic double bond hydrogenation to the dimeric dibasic acid etc..
The fatty acid that the carbon atom number of above-mentioned every 1 carboxyl is 10 or more can be used alone, and can also be used in mixed way 2 kinds More than.
The carbon atom number of the epoxy resin and every 1 carboxyl in 1 molecule with 2 or more epoxy groups is at least the 1 of 8 or more The reaction method of kind fatty acid can be well known method, for example, to above-mentioned epoxy resin in diluent appropriate The reaction method heated with above-mentioned fatty acid.
Ratio (charge ratio of the fatty acid that the carbon atom number of every 1 carboxyl is 8 or more in photoresist containing carboxyl Example) it is not particularly limited, such as from the flexibility and insulating reliability for further increasing solidfied material (especially on thickness direction Insulating reliability) from the aspect of, lower limit value preferably 10 mass %, from the side for reliably improving flexibility and insulating reliability Face consideration, particularly preferred 15 mass %.On the other hand, from by moderately maintaining leading for free-radical polymerised unsaturated monocarboxylic Enter amount and maintain it is excellent it is photosensitive from the aspect of, upper limit value preferably 50 mass %, particularly preferred 40 mass %.
C) free-radical polymerised unsaturated monocarboxylic
The epoxy reaction of epoxy resin in free-radical polymerised unsaturated monocarboxylic and 1 molecule with 2 or more epoxy groups, To import the photo-curable group that can polymerize by the free radical generated using Photoepolymerizationinitiater initiater into epoxy resin. As long as free-radical polymerised unsaturated monocarboxylic assigns the substance of photo-curable to epoxy resin, it is not particularly limited, For example, acrylic acid, methacrylic acid, β-acryloxy propionic, ω-carboxyl-polycaprolactone-(methyl) acrylic acid, Acryloyl group or methylacryloyl can be imported the carboxylic acid of epoxy resin by crotonic acid, cinnamic acid etc..Wherein, preferred propylene Acid, methacrylic acid, particularly preferred acrylic acid.Above-mentioned carboxylic acid can be used alone, and can also be mixed with two or more.
Ratio (charge proportion) of the free-radical polymerised unsaturated monocarboxylic in photoresist containing carboxyl has no especially Limit, for example, from maintain it is excellent it is photosensitive from the aspect of, lower limit value preferably 2.0 mass %, particularly preferred 3.0 matter Measure %.On the other hand, from by moderately maintain every 1 carboxyl carbon atom number be 8 or more fatty acid import volume and obtain From the aspect of obtaining excellent flexibility and insulating properties, upper limit value preferably 10 mass %, particularly preferred 8.0 mass %.
For in 1 molecule with 2 or more epoxy groups epoxy resin and free-radical polymerised unsaturated monocarboxylic it is anti- Induction method is not particularly limited, for example, can enumerate in diluent appropriate to above-mentioned epoxy resin and free-radical polymerised The reaction method that unsaturated monocarboxylic is heated.
D) multi-anhydride
Multi-anhydride with by the carbon atom number of the epoxy resin and every 1 carboxyl be 8 or more at least one kind of fatty acid it is anti- Answer and the hydroxyl that generates and the hydroxyl generated by the reaction of the epoxy resin and free-radical polymerised unsaturated monocarboxylic Base reaction, so that free carboxyl is imported the epoxy resin.It as multi-anhydride, is not particularly limited, can be used full With unsaturated multi-anhydride.For multi-anhydride, for example, the acid anhydrides of following polyacid: succinic acid, maleic acid, Adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3- methyl tetrahydrophthalic acid, 4- methyl tetrahydro neighbour benzene two Formic acid, 3- ethyl tetrahydrophthalic acid, 4- ethyl tetrahydrophthalic acid, hexahydrophthalic acid, 3- methyl hexahydro neighbour's benzene Dioctyl phthalate, 4- methylhexahydrophthaacid acid, 3- ethyl hexahydrophthalic acid, 4- ethyl hexahydrophthalic acid, methyl four Hydrogen phthalic acid, methylhexahydrophthaacid acid, methylene tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic tetrahydro neighbour benzene two Formic acid, trimellitic acid, Pyromellitic Acid and diglycolic acid etc..In addition, above-mentioned acid anhydrides can be used alone, or suitable Degree ground adjustment alkali-developable, and be mixed with two or more.
Ratio (charge proportion) of the multi-anhydride in photoresist containing carboxyl is not particularly limited, for example, from improve alkali From the aspect of developability, lower limit value preferably 5.0 mass %, particularly preferred 8.0 mass %.On the other hand, excellent from obtaining Insulating reliability from the aspect of, upper limit value preferably 25 mass %, particularly preferred 20 mass %.
The acid value of the above-mentioned various photoresists containing carboxyl is not particularly limited, is examined in terms of reliable alkali development Consider, lower limit value preferred 30mgKOH/g, particularly preferred 40mgKOH/g.On the other hand, from preventing from causing to expose by alkaline developer From the aspect of portion's dissolution, the preferred 200mgKOH/g of the upper limit value of acid value, from the moisture-proof and insulation for being reliably prevented solidfied material From the aspect of reliability reduces, particularly preferred 150mgKOH/g.
In addition, being not particularly limited for the matter average molecular weight of the above-mentioned various photoresists containing carboxyl, from solidfied material From the aspect of obdurability and dry to touch, lower limit value preferably 6000, particularly preferred 10000.On the other hand, from smooth Alkali-developable from the aspect of, the upper limit value of matter average molecular weight preferably 200000, particularly preferred 100000.
As commercially available above-mentioned various photoresists containing carboxyl, for example, CYCLOMER-P (ACA) Z-251 (Daicel-Allnex Ltd.), (the above are days by ZCR-1601H, ZAR-2000, ZFR-1122, FLX-2089, ZCR-1569H This chemical drug Co., Ltd.), Ripoxy SP-4621 (Showa Highpolymer Co., Ltd) etc..It can be used alone above-mentioned resin, The above-mentioned resin that can be mixed with two or more.
(B) Photoepolymerizationinitiater initiater
As Photoepolymerizationinitiater initiater, for example, oxime ester system Photoepolymerizationinitiater initiater.Oxime ester system Photoepolymerizationinitiater initiater is that have The compound of oxime ester base.As oxime ester system Photoepolymerizationinitiater initiater, for example, 1,2- acetyl caproyl, 1- [4- (thiophenyl) -2- (O- benzoyl oxime)], ethyl ketone 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -1- (O- acetyl group oxime), 2- (Acetyloxyimino methyl) thioxanthene-9-one, 1,8- acetyl caproyl, 1,8- bis- [9- ethyl -6- nitro -9H- carbazole -3- Base] -, 1,8- bis- (O- acetyl group oximes), 1,8- acetyl caproyl, 1,8- bis- [9- (2- ethylhexyl) -6- nitro -9H- carbazole -3- Base] -, 1,8- bis- (O- acetyl group oximes), (Z)-(9- ethyl -6- nitro -9H- carbazole -3- base) (4- ((1- methoxy propane -2- Base) oxygen) -2- aminomethyl phenyl) ketone O- acetyl group oxime etc..It can be used alone above compound, also can be used of more than two kinds Above compound.
As the Photoepolymerizationinitiater initiater other than oxime ester system Photoepolymerizationinitiater initiater, for example, phenyl bis- (2,4,6- tri- Methyl benzoyl) phosphine oxide, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin n-butylether, benzene Acyloin isobutyl ether, acetophenone, dimethylamino benzoylformaldoxime, 2,2- dimethoxy -2- phenyl acetophenone, 2,2- diethoxy -2- Phenyl acetophenone, 2- methyl -4 '-(methyl mercapto) -2- morpholino propiophenone, 2- benzyl -2- dimethylamino -1- (4- morpholino Phenyl)-butanone -1,2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- hydroxycyclohexylphenylketone, 4- (2- '-hydroxyethoxy Base) phenyl -2- (hydroxyl -2- propyl) ketone, benzophenone, p- phenyl benzophenone, 4,4 '-diethylamino benzophenone, two Chlorobenzophenone, 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 2- amino anthraquinones, 2- methyl thioxanthones, 2- ethyl Thioxanthones, 2-chlorothioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, benzil dimethyl ketal, acetophenone two Methyl ketal, p- dimethyl amino benzoate etc..Can be used alone above compound, can also be used in mixed way 2 kinds with On above compound.
Mixing ratio of the Photoepolymerizationinitiater initiater in the first photosensitive polymer combination is not particularly limited, such as relative to The photoresist (solid component (resin component), similarly hereinafter) of 100 mass parts, preferably 1.0 mass parts~10 mass parts are especially excellent Select 2.0 mass parts~8.0 mass parts.
(C) (methyl) acrylate monomer
(methyl) acrylate monomer is, for example, photopolymerization monomer, is that every 1 molecule at least has 1 polymeric double bond, excellent Select every 1 molecule that at least there is the compound of 2 polymeric double bonds.In order to become the photocuring of the first photosensitive polymer combination It obtains sufficiently and obtains the solidfied material with acid resistance, heat resistance, alkali resistance etc. and use (methyl) acrylate monomer.
(methyl) acrylate monomer is not particularly limited, for example, (methyl) acrylic acid 2- hydroxyl second Ester, (methyl) phenoxyethyl acrylate, diglycol monotertiary (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl -3- phenoxy group Propyl ester, (methyl) octadecyl ester etc. simple functions (methyl) acrylate compounds, 1,4-butanediol two (methyl) propylene Acid esters, 1,6- hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, diethylene glycol (DEG) two (methyl) acrylic acid Ester, NPGA neopentyl glycol adipate two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, two rings penta Base two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, ethylene-oxide-modified di(2-ethylhexyl)phosphate (first Base) two functions such as acrylate, allylation cyclohexyl two (methyl) acrylate, isocyanuric acid ester two (methyl) acrylate (methyl) acrylate compounds, trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, epoxy pronane modification trimethylolpropane Three (methyl) acrylate, three ((methyl) acryloyl-oxyethyl) isocyanuric acid esters, trifunctional carbamate (methyl) third The trifunctionals such as olefin(e) acid ester (methyl) acrylate compounds, double trimethylolpropane four (methyl) acrylate, propionic acid modified two Pentaerythrite five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, six (first of caprolactone modification dipentaerythritol Base) more than the tetrafunctionals such as acrylate, more than tetrafunctional carbamate (methyl) acrylate (methyl) acrylate Compound etc..It can be used alone above compound, the above compound that can also be mixed with two or more.
Mixing ratio of (methyl) acrylate monomer in the first photosensitive polymer combination is not particularly limited, such as Relative to the photoresist of 100 mass parts, preferably 5.0 mass parts~50 mass parts, particularly preferred 10 mass parts~40 mass Part.
(D) epoxide
Epoxide is used to improve the crosslink density of solidfied material, solid to obtain cured coating film with enough mechanical strengths etc. Compound.For epoxide, for example, epoxy resin.As epoxy resin, for example, bisphenol type epoxy Resin, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin (biphenyl phenolic resin varnish type epoxy resin, phenol novolak type Epoxy resin, cresol novolak type epoxy resin etc.), the bisphenol-f type that reacts epichlorohydrin with Bisphenol F, bisphenol S and obtain, Bisphenol-s epoxy resin and ester ring with cyclohexene oxide base, oxidation adamantyl, cyclopentene oxide base etc. Oxygen resin, three (2,3- glycidyl) isocyanuric acid esters, triglycidyl group three (2- hydroxyethyl) isocyanuric acid ester etc. have Triglycidyl isocyanurate, dicyclopentadiene-type epoxy resin, the adamantane type epoxy resin, biphenyl aralkyl of triazine ring Type epoxy resin, phenyl aralkyl-type epoxy resin, biphenyl type epoxy resin etc..It can be used alone above compound, it can also With the above compound being mixed with two or more.
Mixing ratio of the epoxide in the first photosensitive polymer combination is not particularly limited, such as relative to The photoresist of 100 mass parts, preferably 10 mass parts~100 mass parts, particularly preferred 20 mass parts~80 mass parts.
It, can also be according to need other than above-mentioned (A) ingredient~(D) ingredient in the first photosensitive polymer combination Will containing other than (E) delustering agent various composition, for example form the compound of complex compound with copper, colorant, fire retardant, various add Add agent (such as curing catalysts, extender pigment, defoaming agent etc.), non-reactive diluent etc..
The compound of complex compound is formed with copper
The compound of complex compound is formed with copper by containing, to be used as photopolymerization for example in the first photosensitive polymer combination Initiator cooperate oxime ester system's Photoepolymerizationinitiater initiater and film with a thickness of in 10 μm or so situations below, can obtain on copper foil Photonasty it is more excellent and for copper foil have more excellent adhesiveness solidfied material.This is based on the fact that, is inciting somebody to action Photosensitive polymer combination coated on after on copper foil, and the drying process for making the volatile ingredients such as non-reactive diluent volatilize it Afterwards, at least part of the oxime ester system Photoepolymerizationinitiater initiater in photosensitive polymer combination disappears.Especially from copper foil surface Occurs the oxime ester on the copper foil in the case where the film for foring photosensitive polymer combination with several μm~10 μm or so of thickness It is that Photoepolymerizationinitiater initiater disappears, in addition, also there is above-mentioned phenomenon in the case where drying temperature is 70 DEG C~80 DEG C or so or more. On the other hand, in the case where forming the film of photosensitive polymer combination from copper foil surface with 20 μm or so or more of thickness, The disappearance degree of oxime ester system Photoepolymerizationinitiater initiater weakens.In addition, when other than copper foil surface, such as polyimide base material, glass In the case where applying photosensitive polymer combination on the surface of glass epoxy resin substrate etc., the photopolymerization of above-mentioned oxime ester system does not occur and draws Send out the disappearance of agent.The thickness of the film for disappearing in photosensitive polymer combination of above-mentioned oxime ester system Photoepolymerizationinitiater initiater as a result, To occur in the range of several μm~10 μm or so from copper foil surface, it is thus regarded that this is caused by the reaction of copper intervention 's.Also, if oxidation processes are carried out to copper foil surface, the extinction tests of oxime ester system Photoepolymerizationinitiater initiater are not found.Think this Be because, by copper foil surface formed certain thickness more than oxidation overlay film, so as to inhibit it is in above-mentioned drying process, The reaction of copper intervention.As described above, the compound of complex compound is formed with copper by cooperation, to form overlay film on copper foil and press down The reaction of disappearance of above-mentioned oxime ester system Photoepolymerizationinitiater initiater is made, therefore more excellent photonasty and adhesiveness can be obtained.
As long as the compound for forming complex compound with copper can react and be formed the compound of complex compound with copper, It is not particularly limited, for example, nitrogenous heterocyclic compound.Nitrogenous heterocyclic compound is not particularly limited, example The nitrogenous heterocyclic aromatic compound that phenyl ring and the shared a line of nitrogen-containing heterocycle can such as be enumerated and be bonded.
The nitrogenous heterocyclic aromatic compound sharing a line as phenyl ring and nitrogen-containing heterocycle and being bonded, has no special limit It is fixed, such as from from the aspect of reliably obtaining more excellent photonasty and adhesiveness on copper foil, preferably benzoxazoles, tool There are compound (benzoxazoles derivative), benzotriazole, the compound (benzo with BTA skeleton of benzoxazoles skeleton Triazole derivative), benzothiazole, the compound (benzothiazole derivant) with benzothiazole skeleton, benzimidazole, have benzene And the compound (benzimidizole derivatives) of imidazole skeleton.
As benzoxazoles derivative, as long as the compound with benzoxazoles skeleton, is not particularly limited, example 2- mercaptobenzoxazole can such as be enumerated.As benzotriazole derivatives, as long as the compound with BTA skeleton , be not particularly limited, for example, 1,2,3- benzotriazole, 1,2,3- benzotriazole sodium salts, carboxyl benzotriazole, Carboxyl benzotriazole phenyl ester, carboxyl benzotriazole methyl esters, 2- (2'- hydroxyl -5'- aminomethyl phenyl) benzotriazole, 2- (2'- hydroxyl - 3'- tert-butyl -5'- aminomethyl phenyl) -5- chlorobenzotriazole, 2- (2'- hydroxyl -3', 5'- di-tert-pentyl-phenyl) benzotriazole, 2- (2'- hydroxyl -5'- t-octyl phenyl) benzotriazole, 1- [N, N- bis- (2- ethylhexyl) amino methyl] benzotriazole, 2,2 ' - Di-2-ethylhexylphosphine oxide [6- (2H- benzotriazole -2- base) -4- tert-octyl phenol], the tertiary fourth of 6- (2 benzotriazole base) -4- t-octyl -6'- Base -4'- methyl -2,2' methylene bis phenol, 1- [N, N- bis- (2- ethylhexyl) amino methyl] methylbenzotrazole, 2,2 ' - [[(methyl-1 H- benzotriazole -1- base) methyl] imino group] diethanol etc..As benzothiazole derivant, as long as having benzene And the compound of thiazole skeleton, it is not particularly limited, for example, 2-mercaptobenzothiazole, 2- (methyl mercapto) -2- Benzothiazole, thio dodecanoic acid S- benzothiazole -2- base ester, dibenzyl aminodithioformic acid benzothiazole -2- base ester, 1- (1,2- benzisothiazole -3- base) piperazine, N, N- bis- (2- ethylhexyl) -2-[4-morpholinodithio base sulfenamide, 2- (2- hydroxy benzenes Base) benzothiazole, benzothiazolyl be thio-propionic acid, 3- (2-[4-morpholinodithio base is thio) propionic acid, 2- aminobenzothiazole etc..Separately Outside, as benzimidizole derivatives, as long as the compound with benzimidazole skeleton, is not particularly limited, such as can To enumerate 2-mercaptobenzimidazole, 2- sulfydryl -5- methoxybenzimidazol, 2- sulfydryl-carboxy benzimidazole, 1,3- dihydro -1- Phenyl -2H- benzimidazolyl-2 radicals-thioketones, 2- sulfydryl -5- nitrobenzimidazole, 2- sulfydryl -5- aminobenzimidazole etc..Wherein, exist In the case where temperature height in above-mentioned drying process, the volatilization for forming the compound of complex compound with copper becomes problem, it is therefore preferable that More it is difficult to the compound to volatilize such as carboxyl benzotriazole etc..Can be used alone above compound, also can be used 2 kinds with On above compound.
Content of the compound of complex compound in the first photosensitive polymer combination is formed with copper to be not particularly limited, such as Photonasty on copper foil can be reliably obtained following for 10 μm or so from the thickness of film and for the adherency of copper foil Property from the aspect of, relative to the photoresist of 100 mass parts, preferably its lower limit value be 0.10 mass parts, from more reliably From the aspect of the disappearance for inhibiting oxime ester system Photoepolymerizationinitiater initiater, more preferable 0.20 mass parts, particularly preferred 0.30 mass parts.Separately On the one hand, such as from the alkali-developable of the first photosensitive polymer combination, the insulating reliability of its solidfied material etc. consider, phase For the photoresist of 100 mass parts, preferably its upper limit value is 5.0 mass parts, from preventing copper foil from aoxidizing in rear solidification From the aspect of, more preferable 3.0 mass parts, particularly preferred 2.0 mass parts.
Colorant is pigment, pigment etc., is not particularly limited, furthermore it is also possible to use white color agents, blue-colored The arbitrary hues such as agent, green colourant, yellow colorants, violet colorant, black colorant.For above-mentioned colorant, such as Inorganic system's colorant such as the titanium oxide as white color agents, carbon black as black colorant can be enumerated, as green The organic systems coloring such as phthalocyanines system, the anthraquinone system such as the phthalocyanine green of toner and phthalocyanine blue, thunder Austria Nore indigo plant as blue colorant Agent etc..
For fire retardant, for example, phosphorus flame retardant.As phosphorus flame retardant, for example, tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (bis- chloropropyl of 2,3-) ester, tricresyl phosphate (2- chloropropyl) ester, tricresyl phosphate (2,3- bromopropyl) ester, phosphorus Sour three (bromine chloropropyl) esters, 2,3- dibromopropyl -2,3- chloropropyl phosphate, three (tribromo phenyl) phosphates, three (dibromobenzenes Base) phosphate containing halogen system such as phosphate, three (tribromo neopentyl) phosphates；Trimethyl phosphate, triethyl phosphate, tricresyl phosphate fourth The non-halogens aliphatic phosphate esters such as ester, trioctyl phosphate, three butoxyethyl phosphates；Triphenyl phosphate, tricresyl phosphate base Diphenyl, phosphoric acid xylyl phenylester, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, phosphoric acid xylyl diphenyl Ester, tricresyl phosphate (isopropyl phenyl) ester, isopropyl phenyl diphenyl phosphoester, diisopropyl phenyl phenyl phosphate ester, three (front threes Base phenyl) phosphate, three (tert-butyl-phenyl) phosphates, hydroxy phenyl diphenyl phosphoester, octyl diphenyl phosphate etc. be non- Halogen system aromatic phosphoric ester；Three (diethyl) phosphinic acids aluminium, trimethylethyl phosphinic acids aluminium, three (diphenyl) phosphinic acids aluminium, Bis- (diethyl) phosphinic acids zinc, double Methylethyl phosphinic acids zinc, bis- (diphenyl) phosphinic acids zinc, bis- (diethyl) phosphinic acids oxygen Titanium, four (diethyl) phosphinic acids titaniums, double Methylethyl phosphinic acids oxygen titaniums, tetramethyl ethylphosphinic acid titanium, bis- (diphenyl) secondary phosphines Miscellaneous -10- phospho hetero phenanthrene -10- the oxidation of metal salt, the 9,10- dihydro-9-oxy of the hypophosphorous acid such as sour oxygen titanium, four (diphenyl) phosphinic acids titaniums Object (hereinafter referred to as HCA), the addition reaction product of HCA and acrylate, the addition reaction product of HCA and epoxy resin, HCA and The HCA modified version such as addition reaction product of quinhydrones compound, diphenylacetylene phosphine oxide, triphenylphosphine oxide, trialkyl oxygen Change phosphine oxides based compounds such as phosphine, three (hydroxyalkyl) phosphine oxides etc..Wherein, the preferred fire retardant of organic phosphate system.
Various additives
For various additives, can enumerate the defoaming agent of organic silicon-type, hydrocarbon system and acrylic acid series etc., dicyandiamide (DICY) and Its derivative, melamine and its derivative, boron trifluoride-amine complex, organic hydrazides, diaminomaleonitrile (DAMN) and its Curing catalysts, talcum, barium sulfate, aluminium oxide, the hydrogen such as derivative, guanamines and its derivative, amine acid imide (AI) and polyamines Extender pigments such as aluminium oxide, mica etc..
Non-reactive diluent
Non-reactive diluent is for being adjusted viscosity, the drying property of the first photosensitive polymer combination.As non-reaction Property diluent, for example, organic solvent.For organic solvent, for example, the ketones such as methyl ethyl ketone, hexamethylene, first The ester ring types hydro carbons such as alcohols, hexamethylene, the hexahydrotoluenes such as benzene, dimethylbenzene etc. is aromatic hydrocarbon, methanol, isopropanol, cyclohexanol, The cards such as dioxanes, carbitol, the butyl carbitols such as the petroleum such as petroleum ether, naphtha series solvent, cellosolve, butyl cellosolve must Alcohols, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol Esters such as acetic acid esters, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetate etc..Non-reactive diluent is in the first sense Mixing ratio in photosensitive resin composition is not particularly limited, such as relative to the photoresist of 100 mass parts, preferably 5.0 mass parts~100 mass parts, particularly preferred 10~50 mass parts.
, can from insulation is more reliably obtained in addition, as long as the film thickness of first layer is not particularly limited more than 2.0 μm From the aspect of property (insulating reliability especially on thickness direction), preferably 3.0 μm of lower limit value, particularly preferred 5.0 μm. On the other hand, from the aspect of the flexibility for more reliably obtaining cured film, preferably 50 μm of upper limit value, more preferable 40 μm, Particularly preferred 30 μm.In addition, for the film thickness of first layer and the aftermentioned second layer, such as it can use section etc. and surveyed It is fixed.
Next, being illustrated to the second photosensitive polymer combination of the invention.Second photosensitive polymer combination As long as ingredient contain (E) delustering agent, be not particularly limited, for example, containing (A) photoresist, (B) Photoepolymerizationinitiater initiater, (C) (methyl) acrylate monomer, (D) epoxide and (E) delustering agent.Below to the second photosensitive polymer combination Each ingredient is illustrated.
For (A) photoresist, (B) Photoepolymerizationinitiater initiater, (C) (methyl) acrylate monomer and (D) epoxidation It closes object to be not particularly limited, it is, for example, possible to use the substances enumerated in above-mentioned first photosensitive polymer combination, in addition, right In its mixing ratio, such as can also be carried out with range documented by each ingredient for above-mentioned first photosensitive polymer combination Cooperation.Therefore, for (A) photoresist of the second photosensitive polymer combination, (B) Photoepolymerizationinitiater initiater, (C) (methyl) third Each ingredient of olefin(e) acid ester monomer, (D) epoxide can be cooperated and the first photosensitive resin composition with identical mixing ratio The identical compound of object.
(E) delustering agent
By cooperating delustering agent in the second photosensitive polymer combination, the surface shape of the second layer is made to be formed as concavo-convex, from And be roughened (delustring) and reduce glossiness, it therefore, can be to the table for the stepped construction for having first layer and the second layer Face implements roughening, and as a result, it is possible to reduce the glossiness of the surface element of stepped construction.In delustering agent there are organic matting agent with And inorganic flatting agent.As organic matting agent, for example, polyurethane resin, phenolic resin, silicone resin, fluororesin, poly- Polyolefin such as amide, polypropylene etc..Organic matting agent is preferably powdered, its average grain diameter is not particularly limited, such as From the aspect of more reliably reducing glossiness and obtaining screening characteristics, preferably 5.0 μm~100 μm, particularly preferred 10 μm~ 80μm。
In addition, silica, clay, calcium carbonate etc. can be enumerated as inorganic flatting agent.For the flat of inorganic flatting agent Equal partial size is not particularly limited, such as from the aspect of more reliably reducing glossiness and obtaining screening characteristics, preferably 5.0 μ M~100 μm, particularly preferred 10 μm~80 μm.It can be used alone above-mentioned delustering agent, what can also be mixed with two or more is upper State delustering agent.
In above-mentioned delustering agent, from the aspect of more reliably obtaining flexibility, preferred organic matting agent, particularly preferably Polyurethane resin or silicone resin.
Content of the delustering agent in the second photosensitive polymer combination is not particularly limited, such as from more reliably reducing light From the aspect of damp degree, relative to the photoresist of 100 mass parts, lower limit value preferably 10 mass parts, more preferable 20 mass Part, particularly preferred 30 mass parts.On the other hand, the sense from the aspect of obtaining excellent screening characteristics, relative to 100 mass parts Photosensitiveness resin, upper limit value preferably 100 mass parts, more preferable 90 mass parts, particularly preferred 80 mass parts.
In the second photosensitive polymer combination, other than above-mentioned (A) ingredient~(E) ingredient, it can according to need Contain in the same manner as the first photosensitive polymer combination and for example forms the compound of complex compound, colorant, fire retardant, various with copper Additive (such as curing catalysts, extender pigment, defoaming agent etc.), non-reactive diluent etc..
In addition, the film thickness for the second layer is not particularly limited, from the aspect of more reliably reducing glossiness, under Preferably 2.0 μm of limit value, more preferable 3.0 μm, particularly preferred 5.0 μm.On the other hand, from the flexibility for more reliably obtaining cured film From the aspect of, preferably 50 μm of upper limit value, more preferable 40 μm, particularly preferred 30 μm.
In addition, the aggregate value of the film thickness of film thickness and the second layer for first layer is not particularly limited, from more reliably obtaining From the aspect of obtaining insulating reliability and reducing glossiness, preferably 10 μm of lower limit value, particularly preferred 15 μm.On the other hand, from From the aspect of the flexibility for more reliably obtaining cured film, preferably 100 μm of upper limit value, more preferable 60 μm, particularly preferred 50 μ m。
Covering of circuit pattern from printed circuit board etc. consideration, the cured film including first layer and the second layer The 60 ° of gloss values (surface gloss) on surface the low the more preferred, is, for example, less than 70, and preferably 60 hereinafter, particularly preferred 50 or less.
The manufacturing method of above-mentioned the first photosensitive polymer combination and the second photosensitive polymer combination does not limit In specific method, such as it can be kept mixed using three rollers at room temperature after cooperating above-mentioned each ingredient with regulated proportion It closes dispersion and manufactures.Alternatively, it is also possible to be pre-mixed before mixing dispersion using blender as needed.
Next, being illustrated to the example of the manufacturing method of the printed circuit board with insulating coating of the invention.Example Such as, on the printed circuit board with the circuit pattern for being etched and being formed to copper foil, silk-screen printing, flush coater, stick are utilized Coating method well known to painting machine, spreader, scraper plate coating machine, blade coating device, roll coater, gravure coater etc., with required Thickness (such as DRY film thickness be more than 2.0 μm and for 50 μm of situations below under, Wet film thickness is more than 4.0 μm and is 80 μm or less Thickness) the first photosensitive polymer combination for obtaining as described above of coating and form the film of first layer (lower layer).It connects Get off, on the film of first layer (lower layer), utilizes silk-screen printing, flush coater, bar coater, spreader, scraper plate coating machine, scraper Coating method well known to applicator, roll coater, gravure coater etc. (such as in DRY film thickness is more than 2.0 μm with required thickness And be more than 4.0 μm and be 80 μm of thickness below for Wet film thickness in 50 μm of situations below) apply and obtain as described above Second photosensitive polymer combination and the film for forming the second layer (upper layer), thus to obtain the stepped construction of film.
Next, containing organic solvent in the first photosensitive polymer combination and/or the second photosensitive polymer combination Etc. in the case where non-reactive diluents, in order to make non-reactive diluent volatilize, carry out the temperature at 60 DEG C~80 DEG C or so The predrying of lower heating 15 minutes~60 minutes or so, forms inviscid film.
Next, adhering to have becomes light transmission on the film of the stepped construction of coating other than the pad for making circuit pattern Property pattern minus film, from the upper side irradiate ultraviolet light (such as wavelength be 300nm~400nm range).Moreover, using dilute Non-exposed areas corresponding with the pad is removed and film is made to develop by aqueous alkali.For developing method, using gunite, Elution method etc., as used dilute alkaline aqueous solution, for example, the aqueous sodium carbonate of 0.5 mass of mass %~5 %. Next, using the rear solidification of the progress 20 minutes~80 minutes at 130 DEG C~170 DEG C such as drying machine of heated air circulation type, thus It is capable of forming solder resist film as target etc. on a printed circuit, as the insulating coating of photocuring film.
[embodiment]
Next, being illustrated to the embodiment of the present invention, as long as the present invention is not limited to this without departing from its purport A little examples.
Embodiment 1~11, comparative example 1~3
With each ingredient shown in the cooperation of ratio shown in following table 1~3 following table 1~3, made at room temperature using three rollers It mixes dispersion, thus prepares the first photoresist that first layer is used for used in embodiment 1~11, comparative example 1~3 Composition and the second photosensitive polymer combination for the second layer.Moreover, be coated with preparation as follows first is photosensitive Property resin combination and the second photosensitive polymer combination, to make test film.Digital representation matter in following table 1~3 Measure part.In addition, the empty column expression in following table 1~3 is mismatched.
[table 1]
[table 2]
[table 3]
In addition, the details of each ingredient in table 1~3 is as follows.
(A) photoresist
ZAR-2000, ZCR-1569H, FLX-2089: solid state component (resin component) is 65 mass %, Japanese chemical drug strain formula Commercial firm
In addition, ZAR-2000 and ZCR-1569H are to react acrylic acid at least part of the epoxy group of epoxy resin and obtain Epoxy acrylate, react polyacid with the hydroxyl of generation and structure, the i.e. modified by polyacid epoxy acrylate that obtains.
FLX-2089 is to react methacrylic acid at least part of the epoxy group of epoxy resin and obtain epoxy methyl-prop Olefin(e) acid ester, and react the compound with hydroxyl and carboxyl and polyisocyanate compound with the epoxy methacrylates And structure, the i.e. sour modified urethane epoxy methacrylates obtained.
Synthetic resin A
Under the atmosphere of nitrogen air (2:1), by the diethylene glycol monoethyl ether acetic acid esters (hereinafter referred to as " EDGAC ") of 86.45g, The 8- ethyl octadecane diacid (Okamura Oil Mfg. Co., Ltd., SB-20) of 26.54g (6.3 mass parts), 45.35g (10.7 mass Part) behenic acid, the stearic acid of 9.71g (2.3 mass parts), the acrylic acid of 14.36g (3.4 mass parts), 0.65g (0.1 mass Part) triphenyl phasphine (TPP), 0.43g (0.1 mass parts) methoxyhydroquinon (MEHQ) addition have blender, reflux condensing tube 500mL detachable flask, nitrogen air (2:1) was blown into reaction vessel with 0.3mL/ seconds on one side, is added on one side Thermal agitation at 110 DEG C until dissolving.In addition, by 137.65g (32.6 mass parts) biphenyl aralkyl-type epoxy resin (day This chemical drug Co., Ltd., NC-3000, epoxide equivalent 265g/eq~285g/eq) in 59.8g EDGAC solvent it is heated to 80 DEG C, after making its uniform dissolution, put into above-mentioned flask, the heating stirring 15 hours~17 hours at 115 DEG C and reacted, directly Until the acid value of reaction solution becomes 6mgKOH/g or less.42.23g (9.9 mass parts) further are added into the reactant Hydrogenated trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd, HTMAn), and stirred 2 hours at 100 DEG C in air atmosphere ~3 hours.Acid anhydrides is confirmed using FT-IR (infrared spectrophotometer) to disappear.Solid shown in above-mentioned table 1 is obtained as a result, The synthetic resin A that ingredient (resin component) is 65 mass %, acid value is 85mgKOH/g.
(B) Photoepolymerizationinitiater initiater
Oxime ester system Photoepolymerizationinitiater initiater
NCI-831:ADEKA CORPORATION
OXE-02: BASF AG
Photoepolymerizationinitiater initiater other than oxime ester system
Chemcure DETX:Japan Siber Hegner Co., Ltd.
Irgacure 369: BASF AG
(C) (methyl) acrylate monomer
KRM-8296, EBERCRYL8405:Daicel-Allnex Ltd.
(D) epoxide
EPICRON 860:DIC Corporation
NC-3000: Nippon Kayaku K. K
YX-4000HK: Mitsubishi chemical Co., Ltd
(E) delustering agent
RHC-730: Dainichiseika Color Chem
ACE MATT OK412:Evonik Japan Co., Ltd.
EP-2601: Dong Li-DOW CORNING Co., Ltd.
Curing catalysts
DICY-7: Mitsubishi chemical Co., Ltd
Melamine: Nissan Chemical Ind Ltd
Colorant
Lionol Blue FG-7351: Toyo Ink Manufacturing Co., Ltd.
Denka Black: Deuki Kagaku Kogyo Co., Ltd
Extender pigment
Hydilite H-42STV: Showa Denko K. K
The compound of complex compound is formed with copper
CBT-1: north of the city Chemical Co., Ltd.
Non-reactive diluent
EDGAC: Sanyo is melted into product Co., Ltd.
Defoaming agent
KS-66: Shin-Etsu Chemial Co., Ltd
Fire retardant
Exolit OP-935:Clariant Japan Co., Ltd.
Test film production process
In following processes, it is produced on the photocuring for being formed on substrate and being made of first layer (lower layer) and the second layer (upper layer) The test film of the photocuring film of film, i.e. 2 layer structure.
Substrate: Kapton (Nippon Steel & Sumitomo Metal Corporation " ESPANEX ", as conductor copper foil with a thickness of 12 μm, polyimide film with a thickness of 25 μm)
Surface treatment: 5 mass % sulfuric acid treatments
Coating process: being silk-screen printing for first layer, the second layer
DRY film thickness: first layer, the second layer are film thickness shown in above-mentioned table 1~3
Predrying: 80 DEG C, 20 minutes
Exposure: on the film for the stepped construction being made of the first photosensitive polymer combination and the second photosensitive polymer combination Using ORC MANUFACTURING CO., LTD.DI ultraviolet exposure apparatus according " Mns60 " (light source is high-pressure mercury-vapor lamp) with 100mJ/cm2Or 300mJ/cm2It is exposed
Development: the aqueous sodium carbonate of 1 mass %, temperature are 30 DEG C, and injection pressure is 0.2MPa, and developing time is 60 seconds
Solidify afterwards: 150 DEG C, 60 minutes
Assessment item is as follows.
(1) gloss value
Using Japanese electricity Shi Industrial Co., Ltd Grossmeters VG2000 with 60 ° of measurement angle to pass through test film production process system The test film of work is measured.In embodiment, in the case where solidifying 60 ° of gloss values of film surface less than 70, it is judged as solid Change film surface by delustring.
(2) insulating reliability
For the test film made by test film production process, the upper table of the cured coating film of silver will be vapor-deposited on cured coating film Face is connect with anode, and the copper of aforesaid substrate (flexible printed circuit board) is connect with cathode.Next, being in 60 DEG C, humidity In 95% constant temperature and humidity cabinet, apply the voltage of 50V, utilizes Ion transfer test device (IMV Corporation, " MIG- 8600B/128 ") carry out resistance value METHOD FOR CONTINUOUS DETERMINATION.The measurement time started is set as when the voltage that will apply 50V, measurement is until electricity Resistance value is reduced to less than 1.0E+6(1.0×106) time until Q, it is set to the insulation breakdown time, when according to insulation breakdown Between and the benchmark based on following 3 grades and the insulating reliability of thickness direction (Z-direction) is evaluated.
Zero: the insulation breakdown time is 1000 hours or more
△: the insulation breakdown time was 500 hours or more and less than 1000 hour
×: the insulation breakdown time was less than 500 hours
(3) flexibility
For the test film made by test film production process, 180 ° of bending is repeated a number of times by lock seam machine, By visual observation and the crackle of 200 times of optical microphotograph sem observations cured coating film at this time generates situation, time to not cracking Number be measured, the benchmark based on following 4 grades and evaluated.
◎: 20 times or more
Zero: 5~19 times
△: 1~4 times
×: 0 time
The evaluation result of embodiment is shown in above-mentioned table 1,2, the evaluation result of comparative example is shown in table 3.
By above-mentioned table 1,2 it is found that the film thickness in first layer is more than 2 μm, in first layer without delustering agent and the second layer contains In the embodiment of delustering agent, it can obtain that insulating reliability on flexibility and thickness direction is excellent and gloss value reduces, i.e. Surface element is carried out roughening and makes the cured film of glossiness reduction.In addition, the comparison by Examples 1 to 3 and embodiment 4 can Know, if the film thickness of the second layer containing delustering agent is 5 μm or more, compared with the case where film thickness of the second layer is 2 μm, gloss value It further decreases.In addition, by the comparison of embodiment 7 and other embodiments it is found that if by Polyurethane resin powder or silicon tree Cosmetics end is used as delustering agent, then flexibility further increases.In addition, by the comparisons of embodiment 9 and other embodiments it is found that if The synthetic resin A for being imported with long chain fatty acids structure is used as photoresist, then flexibility further increases.
On the other hand, by above-mentioned table 3 it is found that failing in first layer and the second layer in the comparative example 1 containing delustering agent Obtain insulating reliability.In the comparative example 2 that first layer and the second layer are free of delustering agent, solidify 60 ° of gloss of film surface Value is 70, fails to reduce glossiness, so, fail to implement delustring to solidification film surface.It is 2 μm in the film thickness of first layer In comparative example 3, fail to obtain insulating reliability.
Industrial availability
In the present invention, the insulating reliability on flexibility and insulating reliability, particularly thickness direction can be obtained Excellent and surface element is carried out roughening and makes the cured film of glossiness reduction, thus, for example in the covering power for requiring insulating coating And utility value is high in the art of printed circuit boards of the insulating reliability on thickness direction.

Claims (11)

1. a kind of cured film is the cured film for covering the photosensitive polymer combination of printed circuit board,
The cured film have the printed circuit board side first layer and be arranged on the surface of the first layer second Layer, the film thickness of the first layer are more than 2.0 μm and are free of (E) delustering agent, and the second layer contains (E) delustering agent.
2. cured film according to claim 1, wherein
(E) delustering agent contains Polyurethane resin powder or silicone powders.
3. cured film according to claim 1 or 2, wherein
Relative to 100 mass parts of photoresist for the photosensitive polymer combination for forming the second layer, contain 10 mass parts Above and 100 (E) delustering agent below the mass.
4. cured film according to claim 1 or 2, wherein
Relative to 100 mass parts of photoresist for the photosensitive polymer combination for forming the second layer, contain 30 mass parts Above and 80 (E) delustering agent below the mass.
5. cured film according to any one of claim 1 to 4, wherein
60 ° of gloss values for solidifying film surface are less than 70.
6. cured film according to any one of claim 1 to 5, wherein
The film thickness of the second layer is 5.0 μm or more.
7. cured film according to any one of claim 1 to 6, wherein
The cured film is made of the first layer and the second layer.
8. cured film according to claim 7, wherein
The film thickness of the first layer and the second layer adds up to 10 μm or more and 100 μm or less.
9. cured film according to any one of claim 1 to 8, wherein
The first layer be containing (A) photoresist, (B) Photoepolymerizationinitiater initiater, (C) (methyl) acrylate monomer and (D) solidfied material of the first photosensitive polymer combination of epoxide, the second layer are to contain (A) photoresist, (B) Photoepolymerizationinitiater initiater, (C) (methyl) acrylate monomer, (D) epoxide and (E) delustering agent the second photoresist The solidfied material of composition.
10. cured film according to any one of claim 1 to 9 is photocuring film.
11. a kind of printed circuit board, with cured film described in any one of claims 1 to 10.
CN201811105037.5A 2017-09-21 2018-09-21 The photocuring film of photosensitive polymer combination and printed circuit board with the photocuring film Pending CN109541887A (en)

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Application publication date: 20190329