CN106796400A - Laminate structure - Google Patents
Laminate structure Download PDFInfo
- Publication number
- CN106796400A CN106796400A CN201580055745.0A CN201580055745A CN106796400A CN 106796400 A CN106796400 A CN 106796400A CN 201580055745 A CN201580055745 A CN 201580055745A CN 106796400 A CN106796400 A CN 106796400A
- Authority
- CN
- China
- Prior art keywords
- adhesive linkage
- protective layer
- resin
- laminate structure
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
-
- 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
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Offer can meet requirement performance as the dielectric film of flexible printed circuit board, be also suitable for the structure of the technique for forming bending section and installation portion simultaneously.Additionally, it is provided possessing flexible printed circuit board of the solidfied material as diaphragm, such as coating or solder mask.A kind of laminate structure, dry film and flexible printed circuit board using it, the laminate structure have：The adhesive linkage (A) formed by alkali-developable resin combination and the protective layer (B) formed by photosensitive polymer combination formed on adhesive linkage (A); adhesive linkage (A) is A/B=0.5~50 with the ratio of the thickness of protective layer (B), and the developing powder (a) of adhesive linkage (A) is a/b=1.1~100 with the ratio of the developing powder (b) of protective layer (B).
Description
Technical field
The present invention relates to laminate structure, more particularly to can be used as the stepped construction of the dielectric film of flexible printed circuit board
Body, dry film and flexible printed circuit board using it.
Background technology
In recent years, the small-sized slimming of the electronic equipment for being brought with the popularization by smart mobile phone, tablet terminal, gradually opens
Beginning needs the small spatialization of circuit substrate.Purposes therefore, it is possible to bend the flexible printed circuit board of storage expands, for above-mentioned
Flexible printed circuit board, it is also desirable to reliability up to up to now above.
In this regard, at present, as the dielectric film of the insulating reliability for ensuring flexible printed circuit board, widely used bending
Coating of portion's (deflection division) use with the excellent polyimides of the mechanical property such as heat resistance and flexibility as matrix is (for example, ginseng
According to patent document 1,2), installation portion (non-deflected portion) is excellent using electrical insulating property etc. and can carry out the photonasty tree of retrofit
The hybrid technique of oil/fat composition.
That is, the coating with the excellent polyimides of the mechanical property such as heat resistance and flexibility as matrix needs to utilize mould
Punching press is processed, therefore, it is unsuitable for forming fine wiring.Therefore, for needing the chip installation portion of forming fine wiring, it is necessary to part group
Close the alkali development-type photosensitive resin composition (solder resist) that use can be processed using photoetching process.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 62-263692 publications
Patent document 2：Japanese Unexamined Patent Application 63-110224 publications
The content of the invention
Problems to be solved by the invention
In this way, in the manufacturing process of flexible printed circuit board, it has to hindered with formation using the operation for fitting over layer
The hybrid technique of the operation of layer, has that cost-effectivenes and operability are poor.
In this regard, have studied for the dielectric film as solder mask or the dielectric film as coating to be applied to flexible print circuit
Both the solder mask and coating of plate, but the material that can fully meet both requirement performances is also not implemented practical.
Especially for flexible printed circuit board, seek to realize having concurrently the alkali-developable required by the dielectric film as solder mask and make
The raw material of both mechanical properties such as heat resistance and flexibility required by the dielectric film of coating.
Therefore, it is an object of the present invention to provide a kind of structure, it is met as the dielectric film of flexible printed circuit board
Requirement performance, be also suitable for being formed simultaneously the technique of bending section and installation portion, additionally, it is provided possessing its solidfied material as protection
The flexible printed circuit board of film, such as coating or solder mask.
The scheme for solving problem
In order to solve aforementioned problems, it is a feature of the present invention that having：The bonding formed by alkali-developable resin combination
Layer (A) and the protective layer (B) formed by photosensitive polymer combination formed on the adhesive linkage (A), foregoing adhesive linkage (A)
It is A/B=0.5~50, the developing powder (a) of foregoing adhesive linkage (A) and foregoing guarantor with the ratio of the thickness of foregoing protective layer (B)
The ratio of the developing powder (b) of sheath (B) is a/b=1.1~100.
In laminate structure of the invention, foregoing adhesive linkage (A) and foregoing protective layer (B) preferably can be by light irradiations
Patterned.In addition, laminate structure of the invention can be suitable for the deflection division and non-deflected of flexible printed circuit board
In portion at least any one, specifically, in the coating, solder mask and interlayer dielectic for flexible printed circuit board
At least the purposes of any one is useful.
In addition, dry film of the invention is characterised by, at least one side of foregoing laminate structure of the invention is with film branch
Support is protected.
And then, flexible printed circuit board of the invention is characterised by that it possesses dielectric film, and the dielectric film is printed in flexibility
The layer of foregoing laminate structure of the invention is directly formed on brush circuit substrate or stacking is formed with foregoing dry film of the invention
The layer of structure, is patterned by light irradiation, and makes what pattern was disposably formed using developer solution.
It should be noted that in the present invention, " pattern " refers to solidfied material, the i.e. dielectric film of pattern-like.
The effect of invention
In accordance with the invention it is possible to realize meeting the requirement performance as the dielectric film of flexible printed circuit board, be also suitable for together
When formed bending section and installation portion technique laminate structure；And use its dry film；With flexible printed circuit board.
Brief description of the drawings
Fig. 1 is the process chart of of the manufacture method for schematically showing flexible printed circuit board of the invention.
Specific embodiment
Hereinafter, referring to the drawings and embodiments of the present invention are described in detail.
(laminate structure)
Laminate structure of the invention has：The adhesive linkage (A) that is formed by alkali-developable resin combination and in the bonding
The protective layer (B) formed by photosensitive polymer combination formed on layer (A), foregoing adhesive linkage (A) and foregoing protective layer (B)
The ratio of thickness is A/B=0.5~50, the developing powder (a) of foregoing adhesive linkage (A) and the developing powder of foregoing protective layer (B)
B the ratio of () is a/b=1.1~100.
In order that being patterned with alkaline developer, resin combination is needed with alkali-solubility.During for laminate structure,
If using the resin combination of excellent heat resistance in protective layer, being difficult to assign the resin combination of above-mentioned excellent heat resistance
Dissolubility, therefore, developing powder becomes slow, as a result, there is a problem of that patterning becomes difficult.
The present inventor etc. are conceived to the thickness and developing powder of protective layer and adhesive linkage and carry out to solve the problem
Further investigation, as a result finds, by making the ratio and protective layer of the thickness of protective layer and adhesive linkage and the development speed of adhesive linkage
The ratio of degree is respectively in aforementioned range such that it is able to solves aforementioned problems, so far completes the present invention.
That is, find：Used being laminated to using the protective layer of the slow resin combination of developing powder and the protective layer
On adhesive linkage of the resin combination compared to the fast resin combination of developing powder, make the ratio of both thickness and developing powder
Ratio respectively in aforementioned range when, even if the developing powder of protective layer it is slow and be difficult to be patterned by alkali development, with
And there is residue, the developing powder of adhesive linkage is also fast, as a result can completely rinse both, makes the development speed that stepped construction is overall
Spend in the scope for reality.
In order to have both the mechanical properties such as alkali-developable and heat resistance and flexibility better, the ratio of foregoing thickness is A/
B=0.5~50, preferably A/B=1.0~30, more preferably A/B=2.0~10, in addition, the ratio of foregoing developing powder is
A/b=1.1~100, preferably a/b=2.0~50, more preferably a/b=3.0~30.
When the ratio of thickness is below A/B=50, the protective layer (B) with heat resistance is shared in the thickness of laminate structure
Large percentage, therefore, developability is good and can also obtain sufficient heat resistance.In addition, when being more than A/B=0.5, developability
The large percentage of good adhesive linkage (A), therefore, heat resistance is good and can be patterned by alkali development.
The ratio of developing powder in more than a/b=1.1, the protective layer (B) difficult relative to development, adhesive linkage (A)
Developing powder is relative to accelerate, therefore, it is possible to be patterned by alkali development.In addition, when being below a/b=100, adhesive linkage
(A) it is appropriate to the dissolubility of aqueous alkali, pattern form stabilization, therefore each characteristic such as resistance to plating also becomes good.
When laminate structure develops, each layer of protective layer and adhesive linkage is dissolved in the time wanted needed for aqueous alkali to be set
It is developing time [second], when the thickness of each layer is set into thickness [μm], developing powder is represented by following formula.
Developing powder [μm/second]=thickness [μm]/developing time [second]
(protective layer (B))
The composition of the photosensitive polymer combination of protective layer (B) has no particular limits, it is, for example possible to use conduct in the past
It is that solder mask composition is used, comprising containing carboxy resin or photoresist containing carboxyl, the chemical combination with ethylenic unsaturated bond
The photo-curable compositions of thermosetting resin of thing, Photoepolymerizationinitiater initiater and heat reactivity compound；Comprising containing carboxy resin, light product
The photosensitive heat curing resin combination of alkaline agent and heat reactivity compound.
Wherein, protective layer (B) preferably by comprising heat resistance, obdurability it is excellent with imide ring or imide precursor bone
The resin combination of the alkali-solubility resin of frame is formed.
In the present invention, the alkali-solubility resin with imide ring or imide precursor skeleton refers to, with carboxyl, acid anhydrides
The resin of the alkali-solubility such as base group and imide ring or imide precursor skeleton.For imide ring or imide precursor skeleton
It imported into the alkali-solubility resin, it is possible to use known conventional method.Can for example enumerate：Make carboxylic acid anhydride component and amine component
With any one of isocyanate prepolymer composition or both resin obtained from reaction.Imidizate can be entered by hot-imide
OK, it is also possible to carried out by chemical imidization, them can also be applied in combination to manufacture.
Wherein, as carboxylic acid anhydride component, can enumerate：Tetracarboxylic anhydride, tricarboxylic acid anhydride etc., but these acid anhydrides are not limited to,
As long as being with the compound with amino, the anhydride group that NCO reacts and carboxyl, then including including its derivative
To use.In addition, these carboxylic acid anhydride components can be used alone or be applied in combination.
As tetracarboxylic anhydride, for example, can enumerate：Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,
The double O-phthalic acid dianhydrides of 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 4,4 '-oxygen, 1,2,3,4- benzene tertacarbonic acids dianhydride, 3,3 ", 4,
4 "-terphenyl tetracarboxylic dianhydride, 3,3 ' ", 4,4 ' "-quaterphenyl tetracarboxylic dianhydride, 3,3 " ", 4,4 " " -5-linked benzene tertacarbonic acid two
Acid anhydride, methylene -4,4 '-bis- O-phthalic acid dianhydrides, 1,1- ethidines -4,4 '-bis- O-phthalic acid dianhydrides, 2,2- propylidene base -
4,4 '-bis- O-phthalic acid dianhydrides, 1,2- ethylidene -4,4 '-bis- O-phthalic acid dianhydrides, 1,3- trimethylenes -4,4 '-bis- neighbours
Phthalic acid dianhydride, 1,4- tetramethylenes -4,4 '-bis- O-phthalic acid dianhydrides, 1,5- pentamethylenes -4,4 '-bis- O-phthalics
Acid dianhydride, thio -4,4 '-bis- O-phthalic acid dianhydrides, sulfonyl -4,4 '-bis- O-phthalic acid dianhydrides, the double (3,4- bis- of 1,3-
Carboxyl phenyl) -1,1,3,3- tetramethyl siloxanes dianhydride, double (3,4- dicarboxyphenyis) benzene dianhydrides of 1,3-, the double (3,4- bis- of 1,4-
Carboxyl phenyl) benzene dianhydride, double (3,4- di carboxyl phenyloxies) benzene dianhydrides of 1,3-, double (3,4- di carboxyl phenyloxies) benzene two of 1,4-
Double (2- (3,4- the dicarboxyphenyis) -2- propyl group) benzene dianhydrides of acid anhydride, 1,3-, 1,4- are double (2- (3,4- dicarboxyphenyis) -2- propyl group)
Benzene dianhydride, double (3- (3,4- di carboxyl phenyloxies) phenyl) methane dianhydrides, 2,3,6,7- naphthalene tetracarboxylic acids dianhydride, 1,2,5,6- naphthalenes four
Carboxylic acid dianhydride, 3,4,9,10- perylenetetracarboxylic dianhydrides, 2,3,6,7- anthracenes tetracarboxylic dianhydride, 1,2,7,8- phenanthrene tetracarboxylic dianhydride, 1,2,
3,4- butane tetracarboxylics acid dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydride, pentamethylene tetracarboxylic dianhydride, hexamethylene -1,2,3,4-
Tetracarboxylic dianhydride, hexamethylene -1,2,4,5- tetracarboxylic dianhydrides, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, carbonyl -4,4 ' -
Double (hexamethylene -1,2- dicarboxylic acids) dianhydrides, methylene -4,4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydrides, 1,2- ethylidene -4,
4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydrides, 1,1- ethidines -4,4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydride, 2,2- third
Fork base -4,4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydrides, ethylene glycol double (trimelitic dianhydride), 1,2- (ethylidene) be double (partially
Benzenetricarboxylic anhydride), 1,3- (trimethylene) double (trimellitic anhydrides), 1,4- (tetramethylene) double (trimellitic anhydrides), (five is sub- for 1,5-
Methyl) double (trimellitic anhydrides), 1,6- (hexa-methylene) double (trimellitic anhydrides), 1,7- (heptamethylene) double (trimellitic acids
Acid anhydride), 1,8- (eight methylene) double (trimellitic anhydrides), 1,9- (nine methylene) double (trimellitic anhydrides), 1,10- (decamethylene)
Double (trimellitic anhydrides), 1,12- (ten dimethylenes) double (trimellitic anhydrides), 1,16- (ten hexa-methylenes) double (trimellitic acids
Acid anhydride), 1,18- (18 methylene) double (trimellitic anhydrides) etc..
As tricarboxylic acid anhydride, for example, can enumerate：Trimellitic anhydride, core hydrogenated trimellitic anhydride etc..
As amine component, it is possible to use：The diamines such as aliphatic diamine, aromatic diamine；The polyamines such as aliphatic poly ether amines,
But it is not limited to these amine.In addition, these amine components can be used alone or be applied in combination.
As diamines, for example, can enumerate：P-phenylenediamine (PPD), 1,3- diaminobenzenes, 2,4- toluenediamines, 2,5- toluene
1 diamines of benzene nucleus, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 3,4 '-two such as diamines, 2,6- toluenediamines
The diaminodiphenyl ether such as amino-diphenylethers class, 4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl -4,4 '-benzidine,
2,2 '-dimethyl -4,4 '-benzidine, 3,3 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminourea two
Double (the 3- amino of 2 diamines of benzene nucleus such as phenylate, 3,3 '-diamino diphenyl sulfide, 3,4 '-diamino diphenyl sulfide, 1,3-
Aralkyl sulfid) 3 diamines of benzene nucleus such as benzene, double (4- aminophenyl-thioethers) benzene of 1,3-, double (4- aminophenyl-thioethers) benzene of 1,4-,
3,3 '-bis- (3- amino-benzene oxygens) biphenyl, 3,3 '-bis- (4- amino-benzene oxygens) biphenyl, 4,4 '-bis- (3- amino-benzene oxygens) connection
Benzene, 2,2- are double, and (3- (3- amino-benzene oxygens) phenyl propane, 2,2- are double, and (3- (4- amino-benzene oxygens) phenyl propane, 2,2- are double
(double (4 diamines of benzene nucleus such as 4- (4- amino-benzene oxygens) phenyl propane etc. of 4- (3- amino-benzene oxygens) phenyl propane, 2,2-
Aromatic diamine, 1,2- diaminoethanes, 1,3- diaminopropanes, 1,4- diaminobutanes, 1,5- 1,5-DAPs, 1,6- bis-
The aliphatic diamines such as aminohexane, as aliphatic poly ether amines, can enumerate：Polyamine of ethylene glycol and/or propane diols system etc..Separately
Outward, it is as described below, the amine with carboxyl can also be used.
As the amine with carboxyl, can enumerate：3,5- diaminobenzoic acids, 2,5- diaminobenzoic acids, 3,4- diaminourea
The diaminobenzoic acid class such as benzoic acid；Double (3- amino-benzene oxygens) benzoic acid of 3,5-, double (4- amino-benzene oxygens) benzoic acid of 3,5-
Deng amido-phenoxybenzoic acid class；3,3 '-diaminourea -4,4 ' the carboxyl biphenyl compounds such as-dicarboxylate biphenyl；3,3 '-diamino
Double [4- amino -3- the carboxylics of base -4,4 '-dicarboxyl diphenyl methane, 3,3 '-dicarboxyl -4,4 '-diaminodiphenyl-methane, 2,2-
Base phenyl] the carboxyl diphenyl alkane class such as propane；3,3 '-diaminourea -4,4 '-dicarboxydiphenyl ether, 4,4 '-diaminourea -3,3 ' -
The carboxyl diphenyl ether compound such as dicarboxydiphenyl ether；3,3 '-diaminourea -4,4 '-dicarboxyl diphenyl sulfone, 4,4 '-diaminourea -3,
Diphenyl sulfone compounds such as 3 '-dicarboxyl diphenyl sulfone etc..
As isocyanate prepolymer composition, it is possible to use：Aromatic diisocyanate and its isomers, polymer, aliphatic
The diisocyanate such as diisocyanates, ester ring type diisocyanates and its isomers, other general diisocyanate
Class, but it is not limited to these isocyanates.In addition, these isocyanate prepolymer compositions can be used alone or be applied in combination.
As diisocyanate, for example, can enumerate：4,4 '-methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), naphthalene
Diisocyanate, eylylene diisocyanate, biphenyl diisocyanate, diphenyl sulphone (DPS) diisocyanate, the isocyanide of diphenyl ether two
The aromatic diisocyanates such as acid esters and its isomers, polymer, hexamethylene diisocyanate, isophorone diisocyanate
The aliphatic diisocyanate class such as ester, dicyclohexyl methyl hydride diisocyanate；Or hydrogenate aromatic diisocyanate
Ester ring type diisocyanates and isomers or other general diisocyanates.
Alkali-solubility resin with imide ring or imide precursor skeleton described above can have amido link.Its
Can be to make isocyanates and amido link obtained from carboxylic acid reaction, it is also possible to be the amido link as obtained by other reactions.And then,
There can be the key formed by other additions and condensation.
In addition, being imported into the alkali-solubility resin for imide ring or imide precursor skeleton, it is possible to use known
Conventional, the alkali-solubility polymer with any one of carboxyl and anhydride group or both, oligomer, monomer, for example, be by
These known conventional alkali-solubility resinaes individually or with above-mentioned carboxylic acid anhydride component are combined, and with above-mentioned amine/isocyanates
Resin obtained from class reaction.
In the synthesis of this alkali-solubility resin with alkali-solubility group and imide ring or imide precursor skeleton,
Known conventional organic solvent can be used.As above-mentioned organic solvent, as long as will not be with the carboxyanhydrides as raw material, amine
Class, isocyanates reaction, and the solvent of dissolvable these raw materials just have no problem, and are had no particular limits for its structure.
Wherein, from the aspect that the dissolubility of raw material is high, preferably：N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- first
The non-protonic solvents such as base -2-Pyrrolidone, dimethyl sulfoxide (DMSO), gamma-butyrolacton.
For the above-described with the alkali-solubility such as carboxyl or anhydride group group and imide ring or imide precursor bone
The alkali-solubility resin of frame, in order to tackle photoetching process operation, its acid number be preferably 20~200mgKOH/g, more preferably 60~
150mgKOH/g.When the acid number is more than 20mgKOH/g, the dissolubility for alkali increases, and developability becomes good, and then,
The degree of cross linking with the heat curable component after light irradiation is uprised, and therefore, it can obtain sufficient development contrast.In addition, in the acid
It is worth during for below 200mgKOH/g, the PEB after light irradiation described later can be suppressed and ((POST EXPOSURE are bakeed after exposure
BAKE)) the so-called heat atomization in operation, process margin (process margin) becomes big.
In addition, for the molecular weight of the alkali-solubility resin, if it is considered that developability and cured coating film characteristic, then matter is divided equally
Son amount is preferably 1000~100000, more preferably 2000~50000.When the molecular weight is more than 1000, after exposure, PEB
Sufficient resistance to developability can be obtained with solidification physical property.In addition, when molecular weight is less than 100000, alkali-solubility increases, development
Property improve.
Comprising the resin combination with imide ring or the alkali-solubility resin of imide precursor skeleton alkali is produced using light
During agent, generally in addition to alkali-solubility resin, also containing Photobase generator and heat reactivity compound, Photoepolymerizationinitiater initiater is used
When, in addition to alkali soluble resins, the compound also containing Photoepolymerizationinitiater initiater and with ethylenic unsaturated bond.In addition, as tree
Fat composition, can be applied in combination carboxylic polyurethane resin, carboxylic novolac resin etc..
Photobase generator is that molecular structure changes or molecular cleavage by the light irradiation of ultraviolet, visible ray etc.,
Can be used as more than a kind alkaline matter of the catalyst function of the polymerisation of aftermentioned heat reactivity compound so as to generate
Compound.As alkaline matter, for example, can enumerate：Secondary amine, tertiary amine.
As Photobase generator, for example, can enumerate：Alpha-aminoacetophenone compound；Oxime ester compound；With acyloxy imido
Base, N- formylated aromatic series amino, N- acylated aromatics race amino, nitrobenzylamino formic acid ester group, alkoxybenzyl amino first
Compound of the substitution base such as perester radical etc..Wherein, preferably oxime ester compound, alpha-aminoacetophenone compound.As alpha-amido benzene
Ethanone compounds, particularly preferably have more than 2 materials of nitrogen-atoms.
There is benzoin ehter bond, intramolecular is cracked during by light irradiation in the molecule of alpha-aminoacetophenone compound,
Generation plays the alkaline matter (amine) of solidification catalytic action.As the concrete example of alpha-aminoacetophenone compound, it is possible to use：
(4- morpholinyls benzoyl) -1- benzyl -1- dimethylaminopropanecompounds (IRGACURE 369, trade name, BASF JAPAN
LTD. manufacture), 4- (methylthio phenyl formoxyl) -1- methyl isophthalic acids-morpholinyl ethane (IRGACURE 907, trade name, BASF
JAPAN LTD. manufacture), 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- fourths
The commercially available compounds or its solution such as ketone (IRGACURE 379, trade name, BASF JAPAN LTD. manufactures).
As oxime ester compound, as long as the compound that alkaline matter is generated by light irradiation just can be used arbitrarily.
For above-mentioned oxime ester compound, as commercially available product, can enumerate：CGI-325, IRGACURE of BASF JAPAN LTD. manufactures
N-1919, NCI-831 of OXE01, IRGACURE OXE02, ADEKA CORPORATION manufactures etc..Furthermore it is also possible to it is preferred that
There are 2 compounds of oxime ester base using the intramolecular described in No. 4344400 publications of Japanese Patent No..
This Photobase generator can be used alone, it is also possible to use in combination of two or more.Relative to heat reactivity
The mass parts of compound 100, the compounding amount of the Photobase generator in resin combination is preferably 0.1~40 mass parts, more preferably 0.1
~30 mass parts.During for more than 0.1 mass parts, the contrast of the resistance to developability of illumination part/non-irradiation unit can be well obtained
Degree.In addition, when being below 40 mass parts, solidfied material characteristic is improved.
Heat reactivity compound is that have the resin of the functional group of curing reaction by heat, can be enumerated：Epoxy
Resin, multifunctional oxetane compound etc..
Above-mentioned epoxy resin is the resin with epoxy radicals, can arbitrarily use known resin.Specifically, can lift
Go out：There is the multi-functional epoxy with multiple epoxy radicals in 2 the 2 functionality epoxy resin and molecule of epoxy radicals in molecule
Resin etc..It should be noted that can also be 2 hydrogenated functional epoxide compounds.
As above-mentioned epoxy resin, can enumerate：Bisphenol A type epoxy resin, brominated epoxy resin, nobolak type epoxy tree
Fat, bisphenol f type epoxy resin, bisphenol-A epoxy resin, glycidyl amine type epoxy resin, hydantoins type asphalt mixtures modified by epoxy resin
Fat, alicyclic epoxy resin, trihydroxy benzene methylmethane type epoxy resin, di- toluene phenol-type epoxy resin or biphenyl phenolic epoxy
Resin or their mixture；Bisphenol-s epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, four hydroxy phenyl ethane type epoxies
Resin, hetero ring type epoxy resin, o-phthalic acid diglycidyl ester resin, four glycidyl group xylenol ethane resin, contain
Naphthol-based Epoxy Resin, the epoxy resin with dicyclopentadiene skeleton, GMA copolymerization system epoxy resin,
Copolymerization epoxy resin, CTBN modified epoxies of N-cyclohexylmaleimide and GMA etc..
These epoxy resin can be used singly or in combination of two or more.
As the compounding amount of above-mentioned heat reactivity compound, the equivalent proportion (alkali-solubility such as carboxyl with alkali-solubility resin
Group:The heat reactivity such as epoxy radicals group) it is preferably 1:0.1~1:10.By being set to the scope of this mix ratio, development becomes
Well, fine pattern can easily be formed.Above-mentioned equivalent proportion is more preferably 1:0.2~1:5.
As Photoepolymerizationinitiater initiater, it is possible to use known Photoepolymerizationinitiater initiater, for example, can enumerate：Alpha-aminoacetophenone system
Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater, benzoin compound, acetophenone compound, anthraquinone compounds, thiophene
Ton assimilation compound, ketal compound, benzophenone cpd, tertiary amine compound and xanthone compound etc..
In addition, as the compound with ethylenic unsaturated bond, it is possible to use known compound, have：Acrylic acid 2- hydroxyls
The dihydroxypropyl alkyl ester classes such as base ethyl ester, acrylic acid 2- hydroxy propyl esters；Ethylene glycol, methoxyl group TEG, polyethylene glycol, the third two
The mono acrylic ester or diacrylate esters of the glycol such as alcohol；Hexylene glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, three
The polynary acrylic acid such as the polyalcohols such as hydroxyethyl isocyanuric acid ester or their ethylene oxide adduct or propylene oxide adduct
Esters；Ethylene oxide adduct or the expoxy propane addition of acrylic acid benzene oxygen ester, bisphenol a diacrylate and these phenols
Esters of acrylic acids such as thing etc..
(adhesive linkage (A))
As constitute adhesive linkage (A) alkali-developable resin combination, as long as comprising containing phenolic hydroxyl group, mercapto and
More than a kind functional group in carboxyl, the composition of the resin that can be developed with aqueous slkali, it is possible to use light-cured resin group
Compound, it is also possible to use compositions of thermosetting resin.It is preferred that enumerating comprising the compound with more than 2 phenolic hydroxyl group, containing carboxylic
Base resin, the compound with phenolic hydroxyl group and carboxyl, with more than 2 resin combinations of the compound of mercapto, can be with
Use known conventional material.
Specifically, the photo-curable compositions of thermosetting resin as solder mask composition in the past can be for example enumerated, should
Photo-curable compositions of thermosetting resin is included：Containing carboxy resin or photoresist containing carboxyl, with ethylenic unsaturated bond
Compound, Photoepolymerizationinitiater initiater and heat reactivity compound.Alternatively, it is also possible to using comprising carboxylic polyurethane resin, tool
There is the resin combination of resin, Photobase generator and the heat curable component of carboxyl.Above-mentioned resin combination is following composition：Will be by
The alkali that Photobase generator is produced makes polyurethane resin and heat curable component with carboxyl as catalyst using the heating after exposure
Addition reaction is carried out, and unexposed portion is removed using aqueous slkali, thus, it is possible to develop.
As each material for constituting the resin combination used in adhesive linkage (A), except using known conventional material with
Outward, the material used in above-mentioned protective layer (B) can also similarly be used.
In the resin combination used in above-mentioned adhesive linkage (A) and protective layer (B), for the solidfied material obtained by improving
Flexible, dry to touch, can be compounded known conventional macromolecule resin.As this macromolecule resin, can enumerate：Cellulose
System, Polyester, phenoxy resin based polymer, Pioloform, polyvinyl acetal system, polyvinyl butyral resin system, polyamide-based, polyamide
Imide series binder polymer, block copolymer, elastomer etc..The macromolecule resin can be used alone, it is also possible to group
Conjunction uses two or more.
In addition, in the resin combination used in adhesive linkage (A) and protective layer (B), in order to the solidification for suppressing solidfied material is received
The characteristics such as contracting, raising adaptation, hardness, can be compounded inorganic filler.As this inorganic filler, for example, can enumerate：Sulphur
Sour barium, amorphous silica, fused silica, spherical silicon dioxide, talcum, clay, magnesium carbonate, calcium carbonate, aluminum oxide,
Aluminium hydroxide, silicon nitride, aluminium nitride, boron nitride, Nuo Yibao tripoli etc..
In the resin combination used in adhesive linkage (A) and protective layer (B), in order to prepare resin combination, in order to adjust
For coating the viscosity in base material, carrier film, it is possible to use organic solvent.As this organic solvent, can enumerate：Ketone,
Aromatic hydrocarbon, glycol ethers, glycol ethers acetate esters, esters, alcohols, aliphatic hydrocarbon, oil series solvent etc..It is this organic molten
Agent can be used alone, it is also possible to be used in the form of mixture of more than two kinds.
In the resin combination used in adhesive linkage (A) and protective layer (B), coloring can be further compounded as needed
The compositions such as agent, sulfhydryl compound, closely sealed accelerator, antioxidant, ultra-violet absorber.These compositions can use electronic material
Known conventional material in field.Furthermore it is possible to suitable compounding：Fine particle silica, hydrotalcite, organobentonite, montmorillonite
Deng defoamer, levelling agent, silane coupler, the antirust agent of known conventional thickener, silicon-type, fluorine system, macromolecular etc.
Deng such known conventional additive kind.
In laminate structure of the invention, from from the viewpoint of the tracing ability to copper circuit, adhesive linkage (A) is preferably than protection
Layer (B) is thick.
Laminate structure of the invention can be used at least appointing in the deflection division of flexible printed circuit board and non-deflected portion
One, it is preferred for both, thus, it is possible to obtain flexible printed circuit board and the raising for possessing the sufficient durability to bending
Cost-effectivenes and operability.Specifically, laminate structure of the invention can be used for the coating of flexible printed circuit board, welding resistance
At least purposes of any one in layer and interlayer dielectic.
(manufacture method of flexible printed circuit board)
In the present invention, layer direct or that above-mentioned laminate structure is formed by dry film, leads on flexible print circuit base material
Cross light irradiation to be patterned, be disposably patterned to form dielectric film by developer solution such that it is able to obtain flexible printing
Circuit board.The characteristics such as the flexibility of the individual layer of conventional solder mask are poor, but it is manufactured according to the present invention by adhesive linkage (A) and protection
The laminate structure that layer (B) is formed, makes the ratio and protective layer of the thickness of protective layer and adhesive linkage and the development speed of adhesive linkage
The ratio of degree in aforementioned range, can well have both the mechanical properties such as alkali-developable and heat resistance and flexibility respectively.
Hereinafter, on one of the method by laminate structure of the invention manufacture flexible printed circuit board of the invention,
It is middle for both adhesive linkage (A) and protective layer (B) to have used the resin combination containing Photobase generator and heat reactivity compound
Situation, illustrated based on the process chart shown in Fig. 1.It should be noted that conventional as solder mask composition using
It is being used, comprising triggering containing carboxy resin or photoresist containing carboxyl, the compound with ethylenic unsaturated bond, photopolymerization
In the case of the photo-curable compositions of thermosetting resin of agent and heat reactivity compound, can use and solder mask identical work
Sequence.
[lamination process]
Lamination process is the operation that laminate structure of the invention is formed on base material.Lamination process in Fig. 1 is displayed in
It is formed with the flexible print circuit base material 1 of copper circuit 2, the shape of the laminate structure that formation is made up of adhesive linkage 3 and protective layer 4
State, the adhesive linkage 3 is formed by alkali developable resin combination.
Wherein, for each layer of composition laminate structure, for example can be by the tree by adhesive linkage 3 and protective layer 4 is constituted
Oil/fat composition is coated on base material and dries it successively, the method for directly forming adhesive linkage 3 and protective layer 4；Or will constitute
The form that the resin combination of adhesive linkage 3 and protective layer 4 is respectively prepared dry film is sequentially laminated the method in base material to be formed.Separately
Outward, it is also possible to be laminated to the method for base material by the laminate structure that will be made the dry film form of 2 Rotating fields to be formed.Now,
At least one side of laminate structure can also be made with film support or protection.As the film for using, it is possible to use tied from stacking
The strippable plastic sheeting of structure body.Thickness for film has no particular limits, but is fitted generally in the range of 10~150 μm
Preferably select.From from the viewpoint of coating strength, the interface of each interlayer can also be fusion.
Resin combination can be knife type coater, lip coating machine, comma coater, film to the coating method of base material
The known method such as coating machine.In addition, drying means can be to use heated air circulation type drying oven, IR stoves, hot plate, convection oven
Deng the device of the thermal source with the mode of heating using steam, the method for contacting the hot air convection in drying machine；And pass through
Nozzle is blowed to the known method such as method of supporter.
Wherein, as base material, to be pre-formed with the flexible print circuit base material of circuit.In addition, in order to obtain except expectation
Effect beyond other effects, layer can also be further set between adhesive linkage 3 and protective layer 4.
[light irradiation operation]
Light irradiation operation is following operation：Made using light irradiation by the pattern-like with minus contained in resin combination
Photobase generator activation so that illumination part solidify.In the light irradiation operation, mask 5 is configured on protective layer 4, and with negative
The pattern-like of type carries out light irradiation, activates the Photobase generator contained by resin combination, so that illumination part solidifies.
In the operation, Photobase generator destabilization is made due to the alkali generated in illumination part, alkali is produced by Photobase generator
Property material (below, sometimes referred to simply as " alkali "), make Photobase generator destabilization due to the alkali of the generation, and then generate alkali.Recognize
To generate alkali and chemically propagation until the deep of each layer, can cure sufficiently the deep until each layer by with such operation.
During heat cure behind, the alkali is acted as alkali-developable resin with the catalyst of the addition reaction of heat reactivity compound
With, and addition reaction is carried out, therefore, in illumination part, each abundant heat-cure of layer is until deep.Resin combination now
Solidification is the ring-opening reaction of the epoxy for example by thermal response, therefore, can suppress compared with situation about being carried out with light reaction should
Change, cure shrinkage.
As the light irradiation machine used in light irradiation, it is possible to use direct imaging apparatus are (for example, by the CAD from computer
Data are directly with the laser direct imaging device of laser depiction picture), be equipped with the light irradiation machine of metal halide lamp, be equipped with
The light irradiation machine of (super) high-pressure sodium lamp, the light irradiation machine for being equipped with mercury short arc lamp have used (super) high-pressure sodium lamp etc. ultraviolet
The direct imaging apparatus of line lamp.The mask of the light irradiation of pattern-like is the mask of minus.
As active energy beam, laser beam or the scattering of scope of the maximum wavelength in 350~410nm are preferably used
Light.The scope is set to by by maximum wavelength, can activate efficiently Photobase generator.As long as the laser beam using the scope is
Can, for the species of laser, gas laser and Solid State Laser.In addition, its light irradiation amount is different because thickness etc. is different, lead to
100~1500mJ/cm can be often set to2, be preferably set to 300~1500mJ/cm2In the range of.
[heating process]
In heating process, illumination part is solidified by heating, it can be made by the alkali produced in light irradiation operation
It is cured to deep.The heating process is, by caking layer 3 and protective layer 4 after light irradiation operation, to consolidate illumination part
The operation of change, is known as the operation of so-called PEB (bakeing (POST EXPOSURE BAKE) after exposure) operation.Thus, lead to
Crossing the alkali generated in light irradiation operation makes each layer fully solidify until deep, can obtain the excellent patterned layer of curing characteristics.
For example, heating process is preferably, with heat release started temperature or exothermic peak less than non-irradiated resin combination
Temperature and heated higher than the heat release started temperature of resin combination or the temperature of exothermic peak temperature of light irradiation.By such as
This heating only can selectively solidify illumination part.
Wherein, the illumination part heat cure in heating-up temperature preferred resin composition now, but non-irradiation unit does not occur
The temperature of heat cure.Heating-up temperature is, for example, 80~140 DEG C.More than 80 DEG C are set to by making heating-up temperature, can fully be consolidated
Change illumination part.On the other hand, less than 140 DEG C are set to by making heating-up temperature, only can selectively solidify illumination part.Heating
Time is, for example, 10~100 minutes.Heating means are identical with above-mentioned drying means.It should be noted that not given birth in non-irradiation unit
Into the alkali from Photobase generator, therefore, heat cure is inhibited.
[developing procedure]
Developing procedure is to remove non-irradiation unit by alkali development, and forms the patterned layer of minus.Developing procedure in Fig. 1 is
Display makes adhesive linkage 3 and protective layer 4 develop by alkaline aqueous solution, removes non-irradiation unit and forms the work of the patterned layer of minus
Sequence.As developing method, it is possible to use the known method such as infusion process, spray process, spraying process, spread coating.In addition, as development
Liquid, it is possible to use the amine such as potassium hydroxide, NaOH, sodium carbonate, potassium carbonate, sodium phosphate, sodium metasilicate, ammonia, monoethanolamine, tetramethyl
The aqueous alkalis such as base ammonium hydroxide aqueous solution (TMAH) or their mixed liquor.
[the 2nd light irradiation operation]
After developing procedure, the 2nd light irradiation operation is preferably included.2nd light irradiation operation is in order that light irradiation operation
Patterned layer in the unactivated and Photobase generator activation that remains, and generate alkali, as needed the operation of irradiation ultraviolet radiation.2nd
The wavelength and light irradiation amount (light exposure) of the ultraviolet in light irradiation operation can be identical with above-mentioned light irradiation operation, it is also possible to no
Together.Light irradiation amount (light exposure) is, for example, 150~2000mJ/cm2。
[heat curing processes]
After developing procedure, preferably also include heat cure (solidify afterwards) operation.The heat curing processes are in order that patterned layer
Abundant heat cure, carries out the operation of heat cure (solidify afterwards) as needed.After developing procedure, the 2nd light irradiation operation is carried out
In the case of heat curing processes, heat curing processes are preferably carried out after the 2nd light irradiation operation.
The heat curing processes are utilized and produce alkali by light by light irradiation operation or light irradiation operation and the 2nd light irradiation operation
The alkali of agent generation, makes the abundant heat-cure of patterned layer.In heat curing processes, due to having removed non-irradiation unit, thermosetting
Chemical industry sequence can be carried out with temperature more than the curing reaction started temperature of non-irradiated resin combination.Thus, it is possible to make figure
The abundant heat-cure of pattern layer.Heating-up temperature is, for example, more than 150 DEG C.
Embodiment
Hereinafter, using embodiment, further the present invention is described in detail.
(synthesis example 1)
<The synthesis of the alkali-solubility resin with imide ring>
In the removable there-necked flask for being provided with mixer, nitrogen ingress pipe, isocon and condenser pipe, 3,5- bis- is added
Aminobenzoic acid 12.5g, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] propane 8.2g, NMP30g, gamma-butyrolacton 30g, 4,
The double phthalic anhydride 27.9g of 4 '-oxygen, trimellitic anhydride 3.8g, in nitrogen atmosphere, at room temperature, are stirred 4 small with 100rpm
When.Then, toluene 20g is added, distill under 180 DEG C of silicon bath temperature, 150rpm and is removed toluene and water while to stir 4 small
When, obtain the alkali-solubility resin solution containing imide ring.Then, by solid constituent turn into 30 mass % in the way of add γ-
Butyrolactone.The solid constituent acid number of gained resin solution is that 86mgKOH/g, Mw are 10000.
(synthesis example 2)
<The synthesis of carboxylic polyurethane resin>
In the reaction vessel for possessing agitating device, thermometer and condenser, input by 1,5-PD and 1,6- oneself two
PCDL derived from alcohol (Asahi Kasei Chemicals Corporation systems, T5650J, number-average molecular weight
800) 2400g (3 moles), dihydromethyl propionic acid 603g (4.5 moles) and the acrylic acid 2- hydroxyls as monohydroxy compound
Ethyl ester 238g (2.6 moles).Then, put into as the IPDI 1887g (8.5 moles) of polyisocyanates,
Stir and stop while being heated to 60 DEG C, the moment that the temperature in reaction vessel starts to reduce heats again, and with 80 DEG C
Continue to stir, the absorption spectrum (2280cm of NCO is confirmed with infrared absorption spectrum-1) disappear, terminate reaction.Then,
Carbitol acetate is added in the way of solid constituent turns into 50 mass %.The solid constituent of the carboxylic polyurethane resin of gained
Acid number be 50mgKOH/g.
<Constitute the preparation of the resin combination of each layer>
According to the formula shown in table 1 below and table 2, embodiment is compounded respectively and compares the material for exemplifying, and to stir
After machine is pre-mixed, kneaded with triple-roller mill, prepared the resin combination for constituting adhesive linkage and protective layer.Value in table exists
It is just mass parts as long as no special declaration.
<The formation of adhesive linkage (A)>
Preparing the thick 18 μm formation of copper has the flexible print circuit base material of circuit, uses the CB- of Mec Corporation
801Y, carries out pre-treatment.Then, under on the flexible print circuit base material for carried out preceding treatment so that dried thickness turns into
The mode for stating the thickness shown in Tables 1 and 2 is coated with the resin combination of each adhesive linkage.Then, heated air circulation type drying oven is used
It was dried with 80 DEG C/30 minutes, the adhesive linkage (A) that formation is formed by resin combination.It should be noted that on comparative example
1, do not form adhesive linkage.
<The formation of protective layer (B)>
It is coated with the way of making dried thickness as the thickness shown in table 1 below and table 2 on above-mentioned adhesive linkage (A)
Each protective layer used resin combination.Then, it was dried with 80 DEG C/30 minutes with heated air circulation type drying oven, is formed by setting
The protective layer (B) that oil/fat composition is formed.
All 20 μm of the summation of the thickness of adhesive linkage (A) and protective layer (B).
<The measure of thickness>
Thickness is measured using the micrometer MDC-25MX of Mitutoyo Corporation..
<The measure of developing powder>
Each resin combination is coated with the flexible print circuit base material that the thick 18 μm formation of copper has circuit, hot air circulation is used
Formula drying oven was dried with 80 DEG C/30 minutes.Then, the immersed substrate in 30 DEG C, the aqueous sodium carbonate of 1 mass %, surveys
The fixed time dissolved up to film.Developing time [second] will be set to up to the time of film dissolving, thickness is set to thickness [μm]
When, developing powder is represented by following formula.
Developing powder [μm/second]=thickness [μm]/developing time [second]
<Alkali-developable, resistance to soldering heat performance and resistance to gold-plated property>
For the base material for possessing above-mentioned gained laminate structure, with HMW680GW (the metal halogen of ORC CORPORATION
Compound lamp, scatters light), with light exposure 500mJ/cm2, light irradiation is carried out with the pattern-like of minus.Then, heated with 90 DEG C
Treatment 60 minutes.Then, in 30 DEG C, the aqueous sodium carbonate of 1 mass % immersed substrate and carry out 3 minutes develop, evaluate alkali
Developability could.Evaluate with visually carrying out, evaluated according to following benchmark.
○：Can develop without residue
×：There is development residue
Then, it was heat-treated with 150 DEG C/60 minutes using heated air circulation type drying oven, the solidification for obtaining pattern-like is applied
Film.For gained cured coating film, rosin series scaling powder is coated with the evaluation base material, is being redefined for 260 DEG C of solder bath
Middle dipping 20 seconds (10 seconds × 2 times), with isopropanol cleaning scaling powder after, the disbonded test using adhesive tape is carried out, for anti-
Expansion, stripping, the discoloration of layer are lost, is evaluated according to following benchmark.
○：It is completely unconfirmed to change
×：There is expansion, peel off
In addition, for gained cured coating film, bathed using the electroless nickel bath and chemical gilding of commercially available product, 80~90 DEG C,
Plating is carried out under conditions of 5 μm of nickel, 0.05 μm of gold.In the evaluation base material being plated, the infiltration of plating is whether there is with visual valuation.
○：Without infiltration
×：Infiltration is confirmed between base material and film
Acquired results are shown in following Tables 1 and 2s.
[table 1]
※1：The resin of synthesis example 1
※2：The resin of synthesis example 2
※3：Carboxylic novolac resin (acid number 104mgKOH/g, Bis A/ phenol resol resins)
※4：Ethoxylated bisphenol A dimethylacrylates (Xin Zhong villages chemical industry Co. Ltd. system)
※5：Dicyclopentadiene type epoxy resin (Dainippon Ink Chemicals's system)
※6：Bisphenol A type epoxy resin (molecular weight 400) (Mitsubishi chemical Co., Ltd's system)
※7：Oxime type Photobase generator (BASF JAPAN LTD. systems)
※8：2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone
(BASF JAPAN LTD. systems)
※9：Bisphenol-f type acid modified epoxy acrylic ester (Nippon Kayaku K. K's system)
※10：Barium sulfate (Sakai Chemical Industry Co., Ltd.'s system)
[table 2]
Evaluation result shown in above-mentioned Tables 1 and 2 is substantially confirmed：The flexible printed circuit board of embodiment shows
Good developability and heat resistance.On the other hand, it is known that：Comparative example 1 is only by the protection of the resin combination with imide ring
Layer is constituted, therefore, although heat resistance is good, developability is poor, it is impossible to developed using common sodium carbonate.In addition, comparing
In example 2, adhesive linkage is thin, and the ratio of the thickness of adhesive linkage and protective layer deviates the scope of the present invention, therefore, heat resistance is although good
It is good, but result still developability is poor.And then, in comparative example 3, the ratio of the thickness of adhesive linkage and protective layer deviates the present invention
Scope, therefore, although developability is good, result still heat resistance is poor.In comparative example 4, the ratio on thickness, although
Within the scope of the invention, but adhesive linkage is identical with the developing powder of protective layer, the ratio of both developing powders deviates this hair
Bright scope, therefore result still developability is poor.In comparative example 5, the ratio of developing powder deviates the scope of the present invention, because
This, although developability is good, result heat resistance is poor.
Description of reference numerals
1 flexible print circuit base material
2 copper circuits
3 adhesive linkages
4 protective layers
5 masks
Claims (6)
1. a kind of laminate structure, it is characterised in that it has：The adhesive linkage (A) that is formed by alkali-developable resin combination and
The protective layer (B) formed by photosensitive polymer combination formed on the adhesive linkage (A),
The adhesive linkage (A) is A/B=0.5~50 with the ratio of the thickness of the protective layer (B),
The developing powder (a) of the adhesive linkage (A) and the ratio of the developing powder (b) of the protective layer (B) be a/b=1.1~
100。
2. laminate structure according to claim 1, wherein, the adhesive linkage (A) and the protective layer (B) can lead to
Light irradiation is crossed to be patterned.
3. laminate structure according to claim 1, it is used in the deflection division of flexible printed circuit board and non-deflected portion
At least any one.
4. laminate structure according to claim 1, coating, solder mask and interlayer that it is used for flexible printed circuit board
At least purposes of any one in insulating materials.
5. a kind of dry film, it is characterised in that it is at least one side of the laminate structure any one of Claims 1 to 4
With film support or protection.
6. a kind of flexible printed circuit board, it is characterised in that it possesses dielectric film, and the dielectric film is in flexible printed circuit substrate
The layer of the laminate structure any one of upper directly formation Claims 1 to 4 or with the dry film described in claim 5
The layer of laminate structure is formed, is patterned by light irradiation, and obtained from developer solution makes pattern disposably be formed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014210308 | 2014-10-14 | ||
| JP2014-210308 | 2014-10-14 | ||
| PCT/JP2015/078964 WO2016060137A1 (en) | 2014-10-14 | 2015-10-13 | Laminate structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106796400A true CN106796400A (en) | 2017-05-31 |
| CN106796400B CN106796400B (en) | 2020-11-03 |
Family
ID=55746680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580055745.0A Active CN106796400B (en) | 2014-10-14 | 2015-10-13 | Laminated structure |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6374521B2 (en) |
| KR (1) | KR101959648B1 (en) |
| CN (1) | CN106796400B (en) |
| TW (1) | TWI685281B (en) |
| WO (1) | WO2016060137A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110519936A (en) * | 2019-08-01 | 2019-11-29 | 中国电子科技集团公司第二十九研究所 | A kind of the high-precision ultrathin welding resistance film layer and its process for making on ltcc substrate surface |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102173182B1 (en) * | 2018-11-06 | 2020-11-02 | (주)이녹스첨단소재 | flexible photo imageable coverlay film and manufacturing method thereof |
| CN112074099A (en) * | 2020-09-04 | 2020-12-11 | 恒赫鼎富(苏州)电子有限公司 | Preparation method of flexible circuit board insulating layer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1025991A1 (en) * | 1999-02-02 | 2000-08-09 | Agfa-Gevaert N.V. | A method for making positive working printing plates |
| CN101071267A (en) * | 2006-05-08 | 2007-11-14 | 株式会社东进世美肯 | Photoresist composition |
| CN101071266A (en) * | 2006-05-08 | 2007-11-14 | 株式会社东进世美肯 | Photoresist composition |
| TW200905402A (en) * | 2007-03-28 | 2009-02-01 | Jsr Corp | Double-layered film and pattern-forming method using the same, resin composition for forming lower layer of double-layered film, and positive radiation-sensitive resin composition for forming upper layer of double-layered film |
| CN102763036A (en) * | 2010-02-08 | 2012-10-31 | 太阳控股株式会社 | Layered structure and light-sensitive dry film used in same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62263692A (en) | 1986-05-12 | 1987-11-16 | ニツポン高度紙工業株式会社 | Heat-resistant printed wiring board and manufacture of the same |
| JPS63110224A (en) | 1986-10-27 | 1988-05-14 | Dainippon Printing Co Ltd | Flexible overlay film |
| JP2005092037A (en) * | 2003-09-19 | 2005-04-07 | Fuji Photo Film Co Ltd | Ir photosensitive planographic printing original plate |
| TW200728908A (en) * | 2006-01-25 | 2007-08-01 | Kaneka Corp | Photosensitive dry film resist, printed wiring board using same, and method for producing printed wiring board |
| JP4752754B2 (en) * | 2006-12-20 | 2011-08-17 | Ｊｓｒ株式会社 | Two-layer laminated film and pattern forming method using the same |
| JP5615415B2 (en) * | 2012-09-28 | 2014-10-29 | 太陽インキ製造株式会社 | Curable resin composition, composition for forming solder resist, dry film and printed wiring board, laminated structure and method for producing the same |
| JP6147995B2 (en) * | 2012-11-26 | 2017-06-14 | 東京応化工業株式会社 | Forming method of plating model |
| KR102229343B1 (en) * | 2013-04-18 | 2021-03-19 | 다이요 잉키 세이조 가부시키가이샤 | Laminate structure, flexible printed wiring board and method for manufacturing same |
| JP6549848B2 (en) * | 2014-01-17 | 2019-07-24 | 太陽インキ製造株式会社 | Laminated structure |
-
2015
- 2015-10-13 JP JP2016554090A patent/JP6374521B2/en active Active
- 2015-10-13 KR KR1020177012723A patent/KR101959648B1/en active IP Right Grant
- 2015-10-13 WO PCT/JP2015/078964 patent/WO2016060137A1/en active Application Filing
- 2015-10-13 CN CN201580055745.0A patent/CN106796400B/en active Active
- 2015-10-14 TW TW104133692A patent/TWI685281B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1025991A1 (en) * | 1999-02-02 | 2000-08-09 | Agfa-Gevaert N.V. | A method for making positive working printing plates |
| CN101071267A (en) * | 2006-05-08 | 2007-11-14 | 株式会社东进世美肯 | Photoresist composition |
| CN101071266A (en) * | 2006-05-08 | 2007-11-14 | 株式会社东进世美肯 | Photoresist composition |
| TW200905402A (en) * | 2007-03-28 | 2009-02-01 | Jsr Corp | Double-layered film and pattern-forming method using the same, resin composition for forming lower layer of double-layered film, and positive radiation-sensitive resin composition for forming upper layer of double-layered film |
| CN102763036A (en) * | 2010-02-08 | 2012-10-31 | 太阳控股株式会社 | Layered structure and light-sensitive dry film used in same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110519936A (en) * | 2019-08-01 | 2019-11-29 | 中国电子科技集团公司第二十九研究所 | A kind of the high-precision ultrathin welding resistance film layer and its process for making on ltcc substrate surface |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106796400B (en) | 2020-11-03 |
| TW201625078A (en) | 2016-07-01 |
| JPWO2016060137A1 (en) | 2017-06-08 |
| KR101959648B1 (en) | 2019-03-18 |
| WO2016060137A1 (en) | 2016-04-21 |
| JP6374521B2 (en) | 2018-08-15 |
| TWI685281B (en) | 2020-02-11 |
| KR20170069260A (en) | 2017-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI614571B (en) | Laminated structure, flexible printed wiring board and method of manufacturing same | |
| CN105378564B (en) | Photosensitive thermosetting resin composition and flexible printed circuit board | |
| JP6387444B1 (en) | Laminated structure, dry film and flexible printed wiring board | |
| JP6568715B2 (en) | Photosensitive thermosetting resin composition, dry film and printed wiring board | |
| CN106796402A (en) | laminate structure, dry film and flexible printed circuit board | |
| CN105683836B (en) | Photosensitive heat curing resin combination and flexible printed circuit board | |
| CN105683837B (en) | Photosensitive thermosetting resin composition and flexible printed circuit board | |
| CN107850847B (en) | Laminated structure, dry film, and flexible printed circuit board | |
| JP6549848B2 (en) | Laminated structure | |
| JP5903127B2 (en) | Positive photosensitive thermosetting resin composition, dry film and printed wiring board | |
| CN106796400A (en) | Laminate structure | |
| KR102457058B1 (en) | Curable resin composition, laminate structure, cured product thereof, and electronic component | |
| CN105705999A (en) | Photosensitive thermosetting resin composition and flexible printed wiring board | |
| CN105278241A (en) | Photosensitive thermosetting resin composition, dry film and printed wiring board | |
| CN106796395A (en) | Dry film and flexible printed circuit board | |
| JP2019001967A (en) | Curable resin composition, laminate structure, cured product of the same, and electronic component | |
| JP6050180B2 (en) | Laminated structure and flexible printed wiring board | |
| JP6050181B2 (en) | Method for manufacturing flexible printed wiring board and flexible printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230606 Address after: Saitama Prefecture, Japan Patentee after: TAIYO HOLDINGS Co.,Ltd. Address before: Saitama Prefecture, Japan Patentee before: TAIYO INK MFG. Co.,Ltd. |
|
| TR01 | Transfer of patent right |