CN107436536A - The manufacture method of photosensitive polymer combination, dry film and printed circuit board (PCB) - Google Patents
The manufacture method of photosensitive polymer combination, dry film and printed circuit board (PCB) Download PDFInfo
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- CN107436536A CN107436536A CN201710386503.0A CN201710386503A CN107436536A CN 107436536 A CN107436536 A CN 107436536A CN 201710386503 A CN201710386503 A CN 201710386503A CN 107436536 A CN107436536 A CN 107436536A
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- Prior art keywords
- photosensitive polymer
- polymer combination
- film
- methyl
- photoepolymerizationinitiater initiater
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- 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
Abstract
The present invention provides the manufacture method of photosensitive polymer combination, dry film and printed circuit board (PCB), specific provide can highly have both elching resistant and sensitivity and resolution ratio and developability, plyability also excellent photosensitive polymer combination, have the manufacture method of the dry film of the resin bed formed by said composition and the printed circuit board (PCB) of use said composition.A kind of photosensitive polymer combination, it is characterised in that contain：(A) containing carboxy resin, (B) oxime ester system Photoepolymerizationinitiater initiater, the Photoepolymerizationinitiater initiater of (C) in addition to oxime ester system Photoepolymerizationinitiater initiater and (D) multifunctional (methyl) acrylate compounds.
Description
Technical field
The present invention relates to photosensitive polymer combination (following, also referred to as " composition "), dry film and printed circuit board (PCB)
Manufacture method.
Background technology
In the past, the manufacture in printed circuit board (PCB), metal the field such as Precision Machining in, photosensitive polymer combination is used extensively
Make resist, solder resist etc..
It is etched to the method for the circuit forming method as printed circuit board (PCB) in the past.In general, in an etching process, lead to
Cross and form corrosion-resisting pattern on the metals such as copper coin, iron plate, the part not covered by resist layer is removed using etching solution, it is expected
Metal pattern.In addition, the circuit of printed circuit board (PCB) is formed by forming corrosion-resisting pattern on the base material for cover copper and utilizes erosion
Quarter processing forms the method for desired circuit pattern to carry out.
Corrosion-resisting pattern is for example operated and formed as follows.Corrosion-resisting pattern is formed by photoetching process, the photoetching process is to be considered as
Photosensitive resin coating composition on the surface of the base material of etch target, and after making its heated drying or being solidified to form etchant resist,
It is exposed and developing procedure.
In recent years, in printed circuit board (PCB) manufactures industry, it is desirable to the lightweight of printed circuit board (PCB), the high density of conductor circuit
Change, therewith together, it is desirable to form the corrosion-resisting pattern of more fine compared with the past.Correspondingly, to the photonasty of excellent in resolution
The requirement of resin combination also improves.For above-mentioned requirements, develop and used photo development type photosensitive polymer combination, spy
Not being can be using the composition that aqueous alkali is developed (for example, referring to patent document 1).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 1-141904 publications
The content of the invention
Problems to be solved by the invention
Etching solution is highly acid, during accordingly, there exist thinly forming etchant resist to form the corrosion-resisting pattern of fine,
The problem of etchant resist is peeled off because of etching solution.On the other hand, problems be present：When forming etchant resist thicker, although anti-corrosion
Quarter property becomes good, but resolution ratio reduces.In addition, it there is problems：When etchant resist is thicker, formed on base material against corrosion
After pattern, it is difficult to be etched to deep, it is difficult to form desired circuit pattern.
And then sometimes, for the convenience of operation, make the substrate formed with etchant resist overlapping with coated surface and put for a long time
Put.Here, also produce the problem of following new：It is overlapping during in order to form etchant resist and the photosensitive polymer combination using liquid
When coated surface adhere to.
Therefore, it is an object of the present invention to provide can highly have both elching resistant and sensitivity and resolution ratio and show
Shadow, plyability also excellent photosensitive polymer combination, have the dry film of the resin bed formed by said composition and use this
The manufacture method of the printed circuit board (PCB) of composition.
The solution used to solve the problem
The present inventor etc. have made intensive studies to solve above-mentioned problem, as a result find：By addition containing carboxy resin,
Oxime ester system Photoepolymerizationinitiater initiater, the Photoepolymerizationinitiater initiater in addition to oxime ester system Photoepolymerizationinitiater initiater and multifunctional (methyl) third
Enoic acid ester compounds can solve above-mentioned problem, so as to complete the present invention as neccessary composition.
That is, photosensitive polymer combination of the invention is characterised by, is contained：(A) containing carboxy resin, (B) oxime ester system light
Polymerization initiator, the Photoepolymerizationinitiater initiater of (C) in addition to oxime ester system Photoepolymerizationinitiater initiater and (D) multifunctional (methyl) acrylate
Compound.
The photosensitive polymer combination of the present invention is preferably, and foregoing (A) is containing without aromatic rings containing carboxy resin
Carboxy resin.
The photosensitive polymer combination of the present invention is preferably, the light of foregoing (C) in addition to oxime ester system Photoepolymerizationinitiater initiater
Polymerization initiator is acetophenone system Photoepolymerizationinitiater initiater.
The photosensitive polymer combination of the present invention is preferably, and foregoing (D) multifunctional (methyl) acrylate compounds are
Multifunctional (methyl) acrylate compounds being modified through alkylene oxide.
The photosensitive polymer combination of the present invention is preferably, and it is used to form resist.
The dry film of the present invention is characterised by that it, which has, is coated on photosensitive resin combination on film and makes it
Dry the resin bed formed.
The manufacture method of the printed circuit board (PCB) of the present invention is characterised by possessing following process：Film formation process, by before
The surface that photosensitive polymer combination is coated on the foregoing conductor layer of the base material with conductor layer is stated, forms film；Exposure process,
To foregoing film irradiation light, the illumination part of intended shape is formed；Developing procedure, go unless illumination part and implement to pattern；
Etching work procedure, foregoing conductor layer is implemented to etch using patterned foregoing film as resist；Removing step, remove warp
The foregoing film of patterning.
The effect of invention
According to the present invention it is possible to elching resistant and sensitivity and resolution ratio and developability, again can highly be had both by providing
Folded property also excellent photosensitive polymer combination, and the dry film with the resin bed formed by said composition.Particularly, even if
The etchant resist formed by photosensitive polymer combination is film, and elching resistant is also good, and can form the resist pattern of fine
Case.
Embodiment
Hereinafter, embodiments of the present invention are described in detail.
The photosensitive polymer combination of the present invention contains：(A) containing carboxy resin, (B) oxime ester system Photoepolymerizationinitiater initiater, (C)
Photoepolymerizationinitiater initiater and (D) multifunctional (methyl) acrylate compounds in addition to oxime ester system Photoepolymerizationinitiater initiater.Thus, may be used
Have both elching resistant and sensitivity and resolution ratio and developability, plyability also excellent photoresist to be made to height
Composition.
It is anti-corrosion even if etchant resist is film for the etchant resist formed by the photosensitive polymer combination of the present invention
Quarter property is also good, and can form the corrosion-resisting pattern of fine.
The photosensitive polymer combination of the present invention can use in liquid form, can also carry out dry film and use.
Wherein, not via support film as dry film, can filming, therefore from the viewpoint of high sensitivity is excellent, preferably with
The form of liquid uses.In addition, in the case that etchant resist is film or reduces light exposure, it is excellent from sensitivity, resolution ratio
Different aspect is set out, it is also preferred that using in liquid form.
, can also be with by the photosensitive polymer combination of the present invention in liquid form in use, can be preserved with 1 liquid type
More than 2 liquid types preserve.When being preserved more than with 2 liquid types, it is not particularly limited for the group technology of each composition, (B) oxime ester system
Photoepolymerizationinitiater initiater can be contained in any one of the 1st combination thing liquid, the 2nd combination thing liquid.For example, it is segmented into including (A)
The 1st combination thing liquid containing carboxy resin and the 2nd combination thing liquid comprising (B) oxime ester system Photoepolymerizationinitiater initiater.From sensitivity and divide
From the viewpoint of resolution, preferably more than 2 liquid types to preserve, now, (A) is containing carboxy resin and (B) oxime ester system Photoepolymerizationinitiater initiater
It is preferred that preserved with separated liquid type.By using (B) oxime ester system Photoepolymerizationinitiater initiater, L/S=30/30 μm of high score can be obtained
Resolution.However, when (B) oxime ester system's Photoepolymerizationinitiater initiater and (A) are present in 1 liquid type containing carboxy resin, according to preservation state etc.,
(B) oxime ester system Photoepolymerizationinitiater initiater has the possibility of inactivation, because becoming that the characteristic of script can not be played sometimes.With 1
When liquid type preserves, in order to not make curing reaction etc. preferably be preserved at low temperature.
Then, illustrated for each composition of the photosensitive polymer combination of the present invention.It should be noted that this explanation
In book, (methyl) acrylate refers to the term for being referred to as acrylate, methacrylate and their mixture, for it
His similar statement is also same.
[(A) contains carboxy resin]
(A) that photosensitive polymer combination as the present invention contains contains carboxy resin, and can arbitrarily use has carboxyl
Resin, specifically, itself there is the photoresist containing carboxyl of ethylenical unsaturated double bonds and without olefinic insatiable hunger
Contain carboxy resin with double bond.Particularly, as the photosensitive composite for carrying out alkali development, from photo-curable, resistance to developability
Aspect is set out, and has the photoresist containing carboxyl of ethylenical unsaturated double bonds more preferably in molecule.Moreover, its unsaturated double-bond is excellent
Choosing is derived from the double bond of acrylic or methacrylic acid or the derivative from them.
As containing carboxy resin, become better aspect from developability, sensitivity, resolution ratio, plyability, preferably
To contain carboxy resin without aromatic rings.As containing carboxy resin, photonasty, non-photosensitive, but from elching resistant, spirit
From the viewpoint of sensitivity, resolution ratio, preferred photonasty.
As the concrete example containing carboxy resin, the compound being preferably exemplified below (oligomer and polymer).
(1) unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methylstyrene, (methyl) acrylic acid lower are passed through
Contain carboxy resin obtained from the copolymer compounds containing unsaturated group such as Arrcostab, isobutene.
(2) aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, aromatic series are utilized
The carboxylic diol compound such as the diisocyanate such as diisocyanate and dihydromethyl propionic acid, dimethylolpropionic acid and poly- carbon
Acid esters system polyalcohol, polyethers system polyalcohol, polyester-based polyols, polyolefin polyalcohol, acrylic polyol, bisphenol-A system
Diatomic alcohol compounds such as alkylene oxide addition product dihydric alcohol, the compound with phenolic hydroxyl group and alcohol hydroxyl group and as needed
The compound with 1 alcohol hydroxyl group sudden reaction obtained from polyurethane resin containing carboxyl.
(3) diisocyanate and bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol F type epoxy tree are passed through
(the first of 2 functional epoxy resins such as fat, bisphenol-s epoxy resin, di- toluene phenol-type epoxy resin, united phenol-type epoxy resin
Base) the anhydride modified thing of acrylate or part thereof, compound containing carboxylic diol and diatomic alcohol compounds sudden reaction and obtain
The polyurethane resin of photonasty containing carboxyl arrived.
(4) by being added in the synthesis of foregoing (2) or the resin of (3) in (methyl) hydroxyalkyl acrylates equimolecular
Compound with 1 hydroxyl and more than 1 (methyl) acryloyl group carries out containing carboxylic obtained from end (methyl) is acrylated
Base photonasty polyurethane resin.
(5) by adding IPDI and pentaerythrite three in the synthesis of foregoing (2) or the resin of (3)
There is the chemical combination of 1 NCO and more than 1 (methyl) acryloyl group in the reaction with same mole thing equimolecular of acrylate
The polyurethane resin of photonasty containing carboxyl obtained from thing progress end (methyl) is acrylated.
(6) make 2 functions or polyfunctional epoxy resin and (methyl) propylene acid reaction more than it, make the hydroxyl for being present in side chain
The photoresist containing carboxyl that base forms with dibasic acid anhydride addition.Here, epoxy resin is preferably solid.Hereinafter, it is referred to as
Carboxyl acid modified epoxy acrylate.It should be noted that the concrete example as polyfunctional epoxy resin, such as can enumerate：Japan
The material of 0039th section of example of JP 2011-213828 publications.
(7) polyfunctional epoxy resin that the further epoxidation of the hydroxyl of 2 functional epoxy resins obtains is made with epoxychloropropane
With (methyl) propylene acid reaction, and make the hydroxyl of generation and photoresist containing carboxyl obtained from dibasic acid anhydride addition.Here,
Preferred epoxy is solid.
(8) make the dicarboxylic acids such as 2 function oxetane resins and adipic acid, phthalic acid, hexahydrophthalic acid anti-
Should, the primary hydroxyl and the dibasic acid anhydrides such as phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride for making generation add
Into into contain carboxyl polyester resin.
(9) bisphenol-A, Bisphenol F, bisphenol S, novolak phenolics, poly(4-hydroxystyrene), naphthols and aldehydes are made
There is the compound and oxirane, epoxy of multiple phenolic hydroxyl group in the molecule of condensation product of condensation product, dihydroxy naphthlene and aldehydes etc. 1
The alkylene oxides such as propane react, so as to get reaction product with containing unsaturated group monocarboxylic acid react, and make gained reaction product
Photoresist containing carboxyl obtained from being reacted with multi-anhydride.
(10) by making the rings such as compound and ethylene carbonate, propylene carbonate in 1 molecule with multiple phenolic hydroxyl group
Reaction product is reacted with the monocarboxylic acid containing unsaturated group obtained from the reaction of shape carbonate products, and makes gained reaction product
Photoresist containing carboxyl obtained from being reacted with multi-anhydride.
(11) by making in 1 molecules such as epoxide and p-hydroxyphenylethanol in 1 molecule with multiple epoxy radicals extremely
There is the monocarboxylic acids containing unsaturated group such as compound and (methyl) acrylic acid of 1 alcohol hydroxyl group and 1 phenolic hydroxyl group less
Reaction, and make the alcohol hydroxyl group and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, equal benzene four of gained reaction product
Photoresist containing carboxyl obtained from the reaction of the multi-anhydrides such as acid dianhydride, adipic anhydride.
(12) further addition (methyl) glycidyl acrylate, (methyl) third in the resin of above-mentioned (1)~(11) are made
There is the compound of 1 epoxy radicals and more than 1 (methyl) acryloyl group in 1 molecules such as olefin(e) acid Alpha-Methyl ethylene oxidic ester and obtain
The photoresist containing carboxyl arrived.
In the photosensitive polymer combination of the present invention, turn into better from developability, sensitivity, resolution ratio, plyability
Aspect is set out, and preferably above-mentioned (1), being particularly for (12) containing carboxy resin contain carboxy resin without aromatic rings.
As described above there are multiple carboxyls on the side chain of trunk polymer containing carboxy resin, therefore can utilize
Aqueous alkali is developed.
In addition, the above-mentioned acid number containing carboxy resin be preferably 20~200mgKOH/g scope, more preferably 40~
150mgKOH/g scope.When acid number containing carboxy resin is more than 20mgKOH/g, the adaptation of film becomes good, and alkali shows
Shadow becomes good.On the other hand, when acid number is below 200mgKOH/g, the molten of as caused by developer solution exposure portion can be suppressed
Solution, therefore, it is possible to suppress line, to be carefully not different developed liquid with unexposed portion to more than necessary or according to circumstances exposure portion molten
Solution is peeled off, and is capable of the resist of depicting pattern shape well.
In addition, the above-mentioned weight average molecular weight containing carboxy resin is different according to resin matrix, preferably 2000~150000,
More preferably 5000~100000 scope.When weight average molecular weight is more than 2000, non-adhesion behavior is good, the painting after exposure
The moisture-proof of film is good, can suppress film reduction during development, suppress the reduction of resolution ratio.On the other hand, weight average molecular weight is
When less than 150000, developability is good, and storage-stable is also excellent.
Two or more use is can be used alone or combined containing carboxy resin.The photosensitive polymer combination of the present invention contains
There is two or more when containing carboxy resin, such as preferably comprise above-mentioned photoresist containing carboxyl.
[(B) oxime ester system Photoepolymerizationinitiater initiater]
The photosensitive polymer combination of the present invention contains (B) oxime ester system Photoepolymerizationinitiater initiater.By combining following show
(C) Photoepolymerizationinitiater initiater in addition to oxime ester system Photoepolymerizationinitiater initiater, and contain (B) oxime ester system Photoepolymerizationinitiater initiater, Neng Gougao
Degree has both elching resistant and sensitivity and resolution ratio.Formed accordingly, for the photosensitive polymer combination by the present invention against corrosion
For film, even if etchant resist is film, elching resistant is also good, and can form the corrosion-resisting pattern of fine.
As (B) oxime ester system Photoepolymerizationinitiater initiater, the oxime ester of structure division shown in general structure shown below (I) is preferably comprised
It is Photoepolymerizationinitiater initiater, the oxime ester system Photoepolymerizationinitiater initiater even more preferably with carbazole structure.There is carbazole as above-mentioned
The oxime ester system Photoepolymerizationinitiater initiater of structure, the oxime ester system Photoepolymerizationinitiater initiater of dimer can be used.
(B) oxime ester system Photoepolymerizationinitiater initiater can be used alone or combine two or more use.
In logical formula (I), R1Represent hydrogen atom, phenyl, alkyl, cycloalkyl, alkanoyl or benzoyl.R2Represent phenyl, alkane
Base, cycloalkyl, alkanoyl or benzoyl.
R1And R2Shown phenyl can have substituent, as the substituent, such as can enumerate：Carbon number 1~6
Alkyl, phenyl, halogen atom etc..
As R1And R2The alkyl of shown alkyl, preferably carbon number 1~20, more than 1 oxygen can be contained in alkyl chain
Atom.Alternatively, it is also possible to be substituted by more than 1 hydroxyl.
As R1And R2The cycloalkyl of shown cycloalkyl, preferably carbon number 5~8.
As R1And R2The alkanoyl of shown alkanoyl, preferably carbon number 2~20.
R1And R2Shown benzoyl can have substituent, as the substituent, such as can enumerate：Carbon number is 1
~6 alkyl, phenyl etc..
As the oxime ester system Photoepolymerizationinitiater initiater comprising structure division shown in logical formula (I), can enumerate：{ 1- [4- (benzene sulphur
Base) -2- (O- benzoyls oxime)] 1,2- acetyl caproyls, the compound shown in following formula (I-1), 2- (Acetyloxyimino methyl)
Thioxanthene-9-one and 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -1- (O- acetyl oxime) ethyl ketones are with
State oxime ester based compound with carbazole skelton such as compound shown in formula (I-2) etc..
In formula (I-2), R11With the R in logical formula (I)1It is synonymous, R12And R14Separately with the R in logical formula (I)2Together
Justice.R13Represent hydrogen atom, halogen atom, the alkyl of carbon number 1~12, cyclopenta, cyclohexyl, phenyl, benzyl, benzoyl
Base, the alkanoyl of carbon number 2~12, the alkoxy carbonyl of carbon number 2~12 (form the carbon number of the alkyl of alkoxy
For more than 2 when, alkyl can be substituted by more than 1 hydroxyl, and alkyl middle-of-chain can also have more than 1 oxygen atom) or benzene
Epoxide carbonyl.
For this oxime ester system Photoepolymerizationinitiater initiater, such as the exposure for direct imaging, it can improve the present invention's
The sensitivity of photosensitive polymer combination, excellent in resolution, therefore it is preferred that.
In addition, oxime ester system Photoepolymerizationinitiater initiater preferably comprises the oxime ester system Photoepolymerizationinitiater initiater of dimer.As dimer
Oxime ester system Photoepolymerizationinitiater initiater, it is more excellent from the viewpoint of developability, sensitivity, resolution ratio, elching resistant become better
Select the compound shown in following formulas (I-3).
In formula (I-3), R23Represent hydrogen atom, alkyl, alkoxy, phenyl, naphthyl.R21、R22Separately represent hydrogen
Atom, alkyl, alkoxy, halogen group, phenyl, naphthyl, anthryl, pyridine radicals, benzofuranyl, benzothienyl.
Ar represent the alkylidene of singly-bound or carbon number 1~10, ethenylidene, phenylene, biphenylene, sub- pyridine radicals,
Naphthylene, anthrylene, sub- thienyl, furylidene, 2,5- pyrroles-diyl, 4,4 '-talan-diyl, 4,2 '-styrene-
Diyl.
N represents 0~1 integer.
As R23The alkyl of shown alkyl, preferably carbon number 1~17.
As R23The alkoxy of shown alkoxy, preferably carbon number 1~8.
R23Shown phenyl can have substituent, as the substituent, such as can enumerate：Alkyl (preferably carbon number 1
~17), alkoxy (preferably carbon number 1~8), amino, alkyl amino (the preferably carbon number 1~8 of alkyl) or dialkyl group
Amino (the preferably carbon number 1~8 of alkyl) etc..
R23Shown naphthyl can have substituent, as the substituent, can enumerate：With R23Shown phenyl can have
The same group of the above-mentioned substituent that has.
As R21And R22The alkyl of shown alkyl, preferably carbon number 1~17.
As R21And R22The alkoxy of shown alkoxy, preferably carbon number 1~8.
R21And R22Shown phenyl can have substituent, as the substituent, such as can enumerate：(preferably carbon is former for alkyl
Subnumber 1~17), alkoxy (preferably carbon number 1~8), amino, alkyl amino (the preferably carbon number 1~8 of alkyl) or two
Alkyl amino (the preferably carbon number 1~8 of alkyl) etc..
R21And R22Shown naphthyl can have substituent, as the substituent, can enumerate：With R21And R22Shown benzene
The same group of above-mentioned substituent that base can have.
And then in formula (I-3), R21、R23It is separately methyl or ethyl, R22For methyl or phenyl, Ar is single
Key or phenylene, naphthylene or sub- thienyl, n are preferable for 0.
As the compound shown in formula (I-3), particularly preferred following compound (1- [9- ethyls -6- (2- methylbenzene first
Acyl group) -9H- carbazole -3- bases] -1- (O- acetyl oxime) ethyl ketone).
And then the compound shown in following logical formula (II)s can be used.
(in formula, R31And R32The alkyl of carbon number 1~12 is separately represented, M represents S, O or NH, R33、R34、
R35、R36And R37The alkyl of hydrogen atom or carbon number 1~6 is separately represented, m and n represent 0~5 integer.)
Further, it is possible to use the compound shown in following logical formula (III)s.
(in formula, R41Represent the alkyl of carbon number 1~20, the aryl of carbon number 6~30, the virtue of carbon number 7~30
Base alkyl or CN, the hydrogen atom of alkyl, aryl and aryl alkyl can also be by OR41-1、COR41-1、SR41-1、NR41-2R41-3、-
NCOR41-2-OCOR41-3, CN, halogen atom ,-CR41-1=CR41-2R41-3Or CO-CR41-1=CR41-2R41-3Substitution, R41-1、R41-2
And R41-3Separately represent hydrogen atom, the alkyl of carbon number 1~20, the aryl of carbon number 6~30, carbon number 7
~30 aryl alkyl or the heterocyclic radical of carbon number 2~20, R42Represent R42-1Or OR42-1, R42-1Represent carbon number 1~20
Alkyl, the aryl of carbon number 6~30 or the aryl alkyl of carbon number 7~30, the hydrogen of alkyl, aryl and aryl alkyl is former
Son can also be substituted with halogen atoms, R43Represent alkyl, the aryl or carbon atom of carbon number 6~30 of carbon number 1~20
The aryl alkyl of number 7~30, R41、R43、R41-1、R41-2And R41-3The methylene of the alkylene moiety of shown substituent can be by
Unsaturated bond, ehter bond, thioether bond, ester bond, thioester bond, amido link or amino-formate bond interrupt 1~5 time, above-mentioned substituent
Moieties can be branched building block, can be cyclic alkyl, and the alkyl end of above-mentioned substituent can be unsaturated bond, R43Can
To form ring together with adjacent phenyl ring.R44And R45Separately represent R42-1、OR42-1, CN or halogen atom, a and b difference
It independently is 0~3.)
For (B) oxime ester system Photoepolymerizationinitiater initiater, as commercially available product, can enumerate：BASF JAPAN LTD. CGI-
325th, IRGACURE OXE01 ({ 1- [4- (thiophenyl) -2- (O- benzoyls oxime)] } 1,2- acetyl caproyls), IRGACURE OXE02
(1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -1- (O- acetyl oxime) ethyl ketone), ADEKA
CORPORATION N-1919, NCI-831, the TR-PBG-304 of Changzhou Tronly New Electronic Materials Co., Ltd., Japanization
Learn TOE-04-A3 of industrial institute's Co. Ltd. system etc..
(B) compounding amount of oxime ester system Photoepolymerizationinitiater initiater by solid constituent conversion in terms of relative to (A) matter containing carboxy resin 100
Measure part, the ratio of preferably 0.01~20 mass parts, more preferably 0.1~10 mass parts.(B) oxime ester system Photoepolymerizationinitiater initiater
When compounding amount is more than 0.01 mass parts, the photo-curable on copper becomes good, and film is not easily stripped, and elching resistant becomes more
Well.On the other hand, when the compounding amount of (B) oxime ester system Photoepolymerizationinitiater initiater is below 20 mass parts, the photopolymerization of (B) oxime ester system is drawn
The light absorbs of hair agent become good, and deep curability improves, and sensitivity, resolution ratio become better.
[Photoepolymerizationinitiater initiater of (C) in addition to oxime ester system Photoepolymerizationinitiater initiater]
The photosensitive polymer combination of the present invention, which contains the photopolymerization of (C) in addition to oxime ester system Photoepolymerizationinitiater initiater, to be triggered
Agent.As the Photoepolymerizationinitiater initiater of (C) in addition to oxime ester system Photoepolymerizationinitiater initiater, such as can enumerate：Benzophenone series, acetophenone
Usual compound known in system, benzoin ether system, benzil ketals system, acylphosphine oxide system, oxime ether system, titanocenes system etc..Its
In, from the viewpoint of sensitivity and surface cure etc. is improved, preferred acetophenone system.
(C) Photoepolymerizationinitiater initiater in addition to oxime ester system Photoepolymerizationinitiater initiater can be used alone or combine 2 kinds with
Upper use.
As the Photoepolymerizationinitiater initiater of (C) in addition to oxime ester system Photoepolymerizationinitiater initiater, specifically, can enumerate：Double (2,4,
6- trimethylbenzoyls)-phenyl phosphine oxide, 2,4,6- trimethylbenzoy-diphenies-phosphine oxide, 2- methyl isophthalic acids-(4-
Methylthiophenyi) -2- morpholino propane -1- ketone, 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4-
Morpholinyl) phenyl] -1- butanone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls) -1- butanone, benzil dimethyl
Ketal and alpha-hydroxyalkyl benzophenone, wherein, particularly preferably：2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4-
(4- morpholinyls) phenyl] -1- butanone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls) -1- butanone, benzil diformazan
It is at least any of in base ketal and alpha-hydroxyalkyl benzophenone.
(C) compounding amount of the Photoepolymerizationinitiater initiater in addition to oxime ester system Photoepolymerizationinitiater initiater is relative in terms of solid constituent conversion
In (A) mass parts containing carboxy resin 100, the ratio of preferably 0.01~30 mass parts, more preferably 0.1~20 mass parts.
[(D) multifunctional (methyl) acrylate compounds]
The photosensitive polymer combination of the present invention contains (D) multifunctional (methyl) acrylate compounds.(D) it is multifunctional
(methyl) acrylate compounds by irradiate active energy beam carry out photocuring, make resin component insoluble in aqueous alkali,
Or help its insoluble.As this compound, usual known polyester (methyl) acrylate, polyethers (methyl) third can be used
Olefin(e) acid ester, carbamate (methyl) acrylate, carbonic ester (methyl) acrylate, epoxy (methyl) acrylate etc..(D)
Multifunctional (methyl) acrylate compounds improve hydrophily, as a result, from the viewpoint of developability raising, preferably through ring
Siloxane modified multifunctional (methyl) acrylate compounds.
As multifunctional (methyl) acrylate compounds, specifically, can enumerate：(methyl) acrylic acid 2- hydroxyl ethyl esters,
(methyl) acrylic acid 2- hydroxypropyl acrylates, NVP, acryloyl morpholine, methoxyl group tetraethylene glycol (methyl) acrylic acid
Ester, methoxy poly (ethylene glycol) (methyl) acrylate, polyethylene glycol two (methyl) acrylate, N, N- dimethyl (methyl) propylene
Acid amides, N- methylols (methyl) acrylamide, N, N- dimethylaminopropyls (methyl) acrylamide, N, N- dimethylaminoethyls
Base (methyl) acrylate, N, N- dimethylaminopropyls (methyl) acrylate, melamine (methyl) acrylate, diethyl
Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, DPG
Two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, Phenoxyethyl
(methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) cyclohexyl acrylate, (first of glycerin diglycidyl ether two
Base) acrylate, T 55 three (methyl) acrylate, (methyl) isobornyl acrylate, cyclopentadiene list
(methyl) acrylate or cyclopentadiene two (methyl) acrylate；Hexylene glycol, trimethylolpropane, pentaerythrite, double three hydroxyls
Multifunctional (methyl) esters of acrylic acid of the polyalcohols such as methylpropane, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or these
The oxirane of polyalcohol or multifunctional (methyl) esters of acrylic acid of propylene oxide adduct；Polyacid and (methyl) acrylic acid
Monoesters, diester, three esters or polyester more than it of hydroxyalkyl acrylate etc..Wherein, from dry to touch is excellent, sensitivity becomes more
Good aspect is set out, preferably multifunctional (methyl) esters of acrylic acid.In addition, functional group number is preferably 2~6 functions, from resolution
The aspect that rate becomes better is set out, further preferred 2~4 function, particularly preferred 3~4 function.These multifunctional (methyl) third
Enoic acid ester compounds can be used alone or combine two or more use.
(D) compounding amount of multifunctional (methyl) acrylate compounds contains carboxyl in terms of solid constituent conversion relative to (A)
The mass parts of resin 100, the scope of 0.5~45 mass parts is appropriate, and the scope of 0.5~40 mass parts is more appropriate.More officials
When the compounding amount of energy (methyl) acrylate compounds is more than 0.5 mass parts, photo-curable, which assigns effect, becomes good, sensitive
Degree becomes better.When on the other hand, for below 45 mass parts, the dry to touch of film becomes good.And then developability,
Resolution ratio also becomes better.
(colouring agent)
The photosensitive polymer combination of the present invention can be compounded colouring agent.As the concrete example of colouring agent, can enumerate：Phthalocyanine
Indigo plant, phthalocyanine green, iodine are green, dual-azo yellow, leuco crystal violet, titanium oxide, carbon black, the black, solvent blue of naphthalene etc..Colouring agent can use 1
Kind, two or more use can also be combined.
This colouring agent is in terms of solid constituent conversion relative to (A) mass parts containing carboxy resin 100,0.01~5 mass parts
Scope be appropriate.
(organic solvent)
The photosensitive polymer combination of the present invention can be compounded organic solvent.As the concrete example of organic solvent, can enumerate：
The ketone such as the alcohols such as methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, acetone, MEK, methylisobutylketone, ethyl acetate, second
Acid butyl ester, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, acetate of butyl carbitol,
The esters such as propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, propylene carbonate, butyl oxide, tetrahydrofuran, Isosorbide-5-Nitrae-
The aliphatic hydrocarbons such as the ethers such as dioxane, n-hexane, normal heptane, normal octane, benzene,toluene,xylene etc. are aromatic hydrocarbon, and
Halogenated hydrocarbons such as chloroform, carbon tetrachloride etc..Organic solvent can be used alone, and can also combine two or more use.It is organic
Solvent is viscosity etc. when being coated on substrate, carrier film for preparation, the regulation of composition and used.
(defoamer, levelling agent)
The photosensitive polymer combination of the present invention can contain defoamer, levelling agent.As defoamer, levelling agent, can lift
Go out：Usual material known in silicon-type, fluorine system, macromolecular etc..Defoamer, levelling agent can use a kind, can also combine
Two or more is used.
This defoamer, levelling agent in terms of solid constituent conversion relative to (A) mass parts containing carboxy resin 100,0.1~10
The scope of mass parts is appropriate.
(other additives)
The photosensitive polymer combination of the present invention can also be compounded known usual than that described above other as needed
Additive.As other additives, such as can enumerate：Surface tension modifier, surfactant, delustering agent, for adjusting film
The polyester based resin of physical property, polyurethane series resin, vinyl resin, acrylic resin, rubber series resin, wax class etc..This
Kind additive can suitably be adjusted dosage and come in the range of the effect of the present invention is not damaged, obtain the desired effects of additive
Compounding.
The present invention photosensitive polymer combination suitably form printed circuit board (PCB), flexible printed circuit board solder mask, cover
The permanent film such as cap rock, interlayer insulating film, etchant resist is formed, particularly from the excellent aspect of light characteristic, suitably form height
The printed circuit board (PCB) of densification and high graph thinning.The photosensitive polymer combination of the present invention is from forming densification and high graph thinning
Printed circuit board (PCB) from the viewpoint of, be suitable for use as resist formation composition.In addition, the no spy of method for patterning
Other restriction, photosensitive polymer combination of the invention are also suitable for based on laser direct imagings such as h rays direct imagings (HDI)
Patterning.The photosensitive polymer combination of the present invention in addition, can be used for printing-ink, jetted ink, photomask system
Make material, printing making material of drawing a design, the partition wall of plasma display panel (PDP), dielectric pattern, PDP, touch-screen
The occlusion images such as electrode (conductor circuit) pattern, the wiring pattern of electronic unit, conductive paste, conductive film, black matrix etc.
Make.
The photosensitive polymer combination of the present invention, not by support film, can make its filming, thus as dry film
From the viewpoint of high sensitivity is excellent, preferably use in liquid form.In addition, it is film even in etchant resist or reduces exposure
In the case of light quantity, from sensitivity, excellent in resolution aspect, it is also preferred that using in liquid form.Make in liquid form
Used time, can be that 1 liquid type can also be more than 2 liquid types.During more than 2 liquid types preserving, do not have for the group technology of each composition
Especially limitation, (B) oxime ester system Photoepolymerizationinitiater initiater can be contained in any one of the 1st combination thing liquid, the 2nd combination thing liquid.For example,
It is segmented into comprising the 1st combination thing liquid of (A) containing carboxy resin and includes the 2nd composition of (B) oxime ester system Photoepolymerizationinitiater initiater
Liquid.From the viewpoint of sensitivity and resolution ratio, preferably more than 2 liquid types to preserve, now, (A) is containing carboxy resin and (B) oxime ester
It is that Photoepolymerizationinitiater initiater is preferably preserved with separated liquid type.By using (B) oxime ester system Photoepolymerizationinitiater initiater, L/S can be obtained
=30/30 μm of high-resolution.However, in the presence of (B) oxime ester system's Photoepolymerizationinitiater initiater and (A) contain carboxy resin in 1 liquid, root
According to preservation state etc., there is the possibility of (B) oxime ester system Photoepolymerizationinitiater initiater inactivation, this is due to become not playing originally sometimes
Characteristic.When being preserved with 1 liquid type, preferably preserve at low temperature and curing reaction etc. can not be carried out.
In addition, the photosensitive polymer combination of the present invention dry film and can use as follows.
The present invention dry film have by the present invention photosensitive polymer combination be coated on film and make its dry and obtain
The resin bed arrived.Carry out dry film when, by the present invention photosensitive polymer combination with above-mentioned organic solvent diluting with adjust to
Suitable viscosity, pass through comma coater (comma coater), knife type coater, lip coating machine (lip coater), rod
Painting machine (rod coater), extrusion coating machine (squeeze coater), inverse formula coating machine (reverse coater), delivery roll
Coating machine (transfer roll cater), gravure coater (gravure coater), flush coater etc. are in carrier film (support
Body) on paint uniform thickness, generally, at a temperature of 50~130 DEG C dry 1~30 minute, so as to form dry painting
Film.Had no particular limits for coating film thickness, generally, with dried film thickness gauge, 0.1~100 μm, preferably 0.5~
Suitably selected in the range of 50 μm.
As carrier film, plastic sheeting can be used, preferably using the polyester film of polyethylene terephthalate etc.,
The plastic sheetings such as Kapton, polyamidoimide film, polypropylene film, polystyrene film.For carrier film
Thickness has no particular limits, and is generally suitably selected in the range of 0.1~150 μm.
After forming the resin bed formed by the composition of the present invention on a carrier film, in order to prevent the surface attachment dust of film
Deng preferably further in the strippable cover layer of the surface of film stacking.As strippable cover layer, such as poly- second can be used
Alkene film, polytetrafluoroethylene film, polypropylene film, surface treated paper etc..As cover layer, as long as to peel off covering
Less than resin bed and the cover layer of the bonding force of carrier film during film.
It should be noted that in the present invention, the composition of the present invention can be coated with above-mentioned cover layer and makes its drying
So as to form resin bed, carrier film is laminated in its surface.That is, in the present invention, when manufacturing dry film, the group as the coating present invention
The film of compound, any of carrier film and cover layer can be used.
In addition, the photosensitive polymer combination regulation of the present invention is arrived to the viscosity for being suitable to coating method using above-mentioned solvent
Afterwards, it is applied to using the methods of dip coating, flow coat method, rolling method, stick coating method, silk screen print method, curtain coating on base material, about 50
Make organic solvent volatile dry contained in composition (temporarily drying) at a temperature of~90 DEG C, it is dry so as to what cannot be do not formed viscously
Dry film.Here, as dry coating, particularly become better aspect, preferably film from resolution ratio, it is specific and
Speech, preferably 3~20 μm.In addition, the photosensitive polymer combination of the present invention is applied in carrier film, and dries it and formed
Film, batched and obtain dry film, in this case, it is utilized to laminating machine etc. with the film (resin bed) and base of composition
The mode of material contact is fitted on base material, then peels off carrier film, it is possible thereby to form the layer (resin bed) of film on base material.
For example, making these film photocurings by using active energy beam irradiation, solidfied material can be obtained.
, can be with addition to being pre-formed with the printed circuit board (PCB) of circuit, flexible printed circuit board as above-mentioned base material
Enumerate to use and used paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimides, glass cloth/nothing
It is (poly- to spin cloth-epoxy resin, glass cloth/paper-epoxy resin, synthetic fibers-epoxy resin, fluororesin polyethylene polyphenylene oxide
Phenylene oxide) cyanate etc. all grades (FR-4 etc.) of material such as high-frequency circuit copper-clad laminated board copper clad layers
Lamination and Kapton, PET film, glass substrate, ceramic substrate, wafer board etc..
Being coated with the volatile dry carried out after the photosensitive polymer combination of the present invention can be carried out with the following method：Use
Heated air circulation type drying oven, IR stoves, hot plate, convection oven etc. have the device of the thermal source of the air mode of heating using steam,
The method for contacting the hot air convection in drying machine；Blowed with by nozzle to the method for supporter.
The exposure machine used in being irradiated as active energy beam, as long as to carry high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal
Halide lamp, mercury short arc lamp etc. and the device for irradiating the ultraviolet of 350~450nm scope, further, it is also possible to use
Direct drawing apparatus (such as by the CAD data direct irradiation active energy beam from computer come the direct of depiction picture
Imaging device).As the light source of machine is directly retouched, as long as being used in the light for the scope that maximum wavelength is 350~410nm.With
It is different according to thickness etc. in the light exposure for forming image, it can generally be 3~500mJ/cm2, be preferably 3~300mJ/cm2
In the range of.
In addition, as developing method, infusion process, spray process, spray-on process, spread coating etc. can be used, can as developer solution
To use the aqueous alkali of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium metasilicate, ammonia, amine etc..
In addition, the manufacture method of the printed circuit board (PCB) of the present invention is characterised by possessing following process：Film forms work
Sequence, photosensitive polymer combination is coated on to the surface of the conductor layer of the base material with conductor layer, forms film；Exposure process,
To film irradiation light, the illumination part of intended shape is formed；Developing procedure, go unless illumination part and implement to pattern；Etching
Process, conductor layer is implemented to etch using patterned film as resist；Removing step, remove patterned painting
Film.
In the present invention, the preferred copper of constituent material of conductor layer, other metal materials such as gold, silver can also be used.In addition, can
Using only in material of the one side formed with conductor layer of base material, can also use in two of the two sides of base material formed with conductor layer
The material of face structure.At this point it is possible to patterning described later is implemented to the conductor layer formed on two sides.In addition, as using photosensitive
Property resin combination form the condition of film, can be formation condition identical condition with above-mentioned dry coating.
As the development conditions in the light irradiation condition and developing procedure in exposure process, can be and above-mentioned active-energy
The irradiation condition and development conditions identical condition of ray.
As the etching condition in etching work procedure, known condition can be used, such as base material is impregnated in copper chloride erosion
Carve in liquid 5~30 minutes or so, there is the conductor layer of patterns of openings corresponding with the patterns of openings of film thus, it is possible to be formed.
As the minimizing technology of the film in removing step, can use film dissolve stripper remove film from base material and
Manufacture the printed circuit board (PCB) formed with circuit.
Stripper, preferably aqueous slkali are dissolved as film, is preferably the aqueous solution of alkalescence.Thereby, it is possible to easily enter
Row dissolving is peeled off.For example, dissolving stripper as etchant resist, sodium hydrate aqueous solution can be used.The concentration of sodium hydroxide is excellent
Elect 0.01~5% as.The concentration of sodium hydroxide is particularly preferably 0.5~3%.Now, dissolving stripping becomes good.Need to illustrate
, as aqueous slkali, the organic solvent comprising alkaline components can be used, the alkaline water containing organic solvent can also be used
Solution.As stripper, such as can enumerate：The inorganic alkali composition such as sodium hydroxide, potassium hydroxide, tertiary amine, quaternary ammonium salt etc. is organic
Alkali composition is dissolved in solution obtained from water, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE or their mixed solution.
The temperature of stripper is for example preferably 30~60 DEG C.As the stripping means using stripper, can enumerate：Spraying
Method, spray process, slurry processes etc..
Embodiment
Hereinafter, show that the present invention is specifically described for embodiment and comparative example, but the present invention is not by following embodiments
Limitation.It should be noted that following, " part " and " % " is quality criteria in case of no particular description.
(synthesis example 1：Solution containing carboxy resin 1)
In the flask for possessing thermometer, mixer, dropping funel and reflux condenser, using as the DPG of solvent
The mass parts of monomethyl ether 325.0 are heated to 110 DEG C, the mass parts of methacrylic acid 174.0 are added dropwise with 3 hours, 6-caprolactone is modified first
The mass parts of base acrylic acid (mean molecule quantity 314) 174.0, the mass parts of methyl methacrylate 77.0, dipropylene glycol monomethyl ether
222.0 mass parts and as polymerization catalyst peroxidating (2 ethyl hexanoic acid) tert-butyl ester (NOF CORPORATION systems,
Perbutyl O) 12.0 mass parts mixture, and then with 110 DEG C stir 3 hours, inactivate polymerization catalyst, obtain resin
Solution.After the resin solution is cooled down, the Daicel Corporation of 289.0 mass parts of addition CYCLOMER M100,
The mass parts of triphenylphosphine 3.0 and the mass parts of hydroquinone monomethyl ether 1.3, are warming up to 100 DEG C, and the open loop that epoxy radicals is carried out by stirring adds
Into reaction, the solution containing carboxy resin 1 as photonasty copolymer resins solution is obtained.
The solid component concentration for so operating obtained solution containing carboxy resin 1 is 45.5 mass %, the acid number of solids
For 79.8mgKOH/g.
(synthesis example 2：Solution containing carboxy resin 2)
The diethyl two as solvent is added in the flask for possessing thermometer, mixer, dropping funel and reflux condenser
Alcohol monoethyl ether acetate, the azodiisobutyronitrile as catalyst, in a nitrogen atmosphere, 80 DEG C are heated to, with about 2 hours
It is added dropwise methacrylic acid and methyl methacrylate with 0.40:The monomer that 0.60 mixed in molar ratio forms.And then stirred
After mixing 1 hour, temperature is improved to 115 DEG C, it is inactivated and is obtained resin solution.
By the resin solution cool down after, using as the four butyl bromation amine of catalyst in 95~105 DEG C, the bar of 30 hours
Under part, the carboxyl for making butyl glycidyl ether and gained resin with 0.40 mol ratio carries out addition reaction, cooling.
And then relative to the OH bases of above-mentioned gained resin, under conditions of 95~105 DEG C, 8 hours, with 0.26 mole
Than making tetrabydrophthalic anhydride carry out addition reaction.Taken out after being cooled to, obtain solution containing carboxy resin 2.
The solid component concentration for so operating obtained solution containing carboxy resin 2 is 50 mass %, the acid number of solid constituent
For 78.1mgKOH/g, weight average molecular weight 35000.
(synthesis example 3：Solution containing carboxy resin 3)
O-cresol phenolic epoxy varnish (Dainippon Ink Chemicals is put into diethylene glycol monoethyl ether acetic acid esters 600g
System, EPICLON N-695,95 DEG C of softening point, epoxide equivalent 214, average functional group number 7.6) 1070g (glycidol radix (virtues
Fragrant ring sum)：5.0 moles), acrylic acid 360g (5.0 moles) and quinhydrones 1.5g, be heated to 100 DEG C and be stirred, make its equal
Even dissolving.Then, triphenylphosphine 4.3g is put into, 110 DEG C is heated to and carries out 2 hours after reacting, be warming up to 120 DEG C, further enter
Row reacts for 12 hours.Fragrant family hydrocarbon (Solvesso 150) 415g, tetrabydrophthalic anhydride are put into gained reaction solution
456.0g (3.0 moles), reaction 4 hours is carried out with 110 DEG C, cooling, is obtained molten as cresol novolak type photoresist
The solution containing carboxy resin 3 of liquid.
The solid component concentration for so operating obtained solution containing carboxy resin 3 is 65 mass %, the acid number of solid constituent
For 89mgKOH/g.
<The preparation of the photosensitive polymer combination of embodiment 1~10 and comparative example 1>
According to the composition shown in ratio (mass parts) the compounding table 1 below and 2 shown in table, premixed using mixer
After conjunction, make it scattered with triple-roller mill, be kneaded, prepare composition respectively.Compounding amount in table represents mass parts.
[table 1]
*1：Photonasty copolymer resins containing carboxyl (synthesis example 1) without aromatic rings, the mass % of solid component concentration 45.5
*2：Photonasty copolymer resins containing carboxyl (synthesis example 2) without aromatic rings, the mass % of solid component concentration 50
*3：Cresol novolak type photonasty (synthesis example 3) containing carboxy resin, the mass % of solid component concentration 65
*4：2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls) -1- butanone, (BASF of IRGACURE 369
JAPAN LTD. systems)
*5：1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, IRGACURE2959
(BASF JAPAN LTD. systems)
*6：Trimethylolpropane EO is modified (n ≈ 1) triacrylate, M-350 (Toagosei Co., Ltd's system), 3 functions
*7：Dipentaerythritol acrylate (Nippon Kayaku K. K's system), the mixture of 5 functions and 6 functions
*8：4,4 ', 4 "-methine three (N, accelerine)
*9：Silicon-type, KS-66 (Shin-Etsu Chemical Co., Ltd.s system)
*10：1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -1- (O- acetyl oxime) ethyl ketone,
IRGACURE OXE02 (BASF JAPAN LTD. systems)
*11：TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.'s system)
*12：N-1919 (ADEKA CORPORATION systems)
*13：TOE-04-A3 (Japan Chemical Industry institute Co. Ltd. system)
*14：C.I.Solvent Blue5, OIL BLUE613 (Orient Chemical Industries Co., Ltd.s
System)
*15：Propylene glycol methyl ether acetate
*16：1st combination thing liquid total amount combines thing liquid total amount with 1 with the 2nd:1 mixing
[table 2]
According to evaluating below the composition of each embodiment of gained and comparative example.It the results are shown in above-mentioned table.
<Developability>
Prepare following substrates：Using silk-screen printing by the photosensitive polymer combination of each embodiment and comparative example formed with
Whole face coating is carried out in a manner of dry film thickness turns into 10 μm on the copper clad laminate of pattern, in 80 DEG C of hot-blast circulation dry furnace
The substrate obtained by drying time was changed with 10 minutes intervals respectively.The substrate is water-soluble by 30 DEG C of 1 mass % sodium carbonate
Liquid with spray 0.2MPa carry out development 90 seconds, research temporarily it is dried development the life-span (life) (can develop it is most long dry when
Between).Metewand is as follows.Acquired results are shown in above-mentioned table 1,2.
○：After drying time is the drying of more than 40 minutes, it can develop
△：Drying time be the drying less than 40 minutes in 10 minutes after, can develop
×：After drying time is the drying less than 10 minutes, it can develop
<Plyability>
Using silk-screen printing by the photosensitive polymer combination of each embodiment and comparative example on multiple copper clad laminates with dry
Dry thickness carries out whole face coating as 10 μm of mode, is dried in 80 DEG C of hot-blast circulation dry furnace 30 minutes.Make to do
Coated face after dry is overlapping with dried coated face, applies 0.5Kg/cm2Load place 48 hours.Visual valuation film
Adhesion.Metewand is as follows.Acquired results are shown in above-mentioned table 1,2.
○：Without adhesion
△：A part is without adhesion
×：There is adhesion in whole face
<Sensitivity>
The photosensitive polymer combination of each embodiment and comparative example is being formed into figuratum copper foil base using silk-screen printing
Whole face coating is carried out in a manner of dry film thickness turns into 10 μm on plate, 30 points are dried in 80 DEG C of hot-blast circulation dry furnace
Clock.Stouffer Corporation T4105C stage exposure meter is loaded on film after the drying, uses ORC
MANUFACTURING CO., LTD. metal halide lamp carry out 40mJ/cm2Exposure, with 30 DEG C of 1 mass % of spraying
Aqueous sodium carbonate 90 seconds, thus removes unexposed portion.The luminous sensitivity of photosensitive polymer combination is formed by determining
The hop count of the stage exposure meter of photocuring film on copper-clad base plate evaluates (the higher expression light of hop count of the stage exposure meter
Sensitivity is higher).Metewand is as follows.Acquired results are shown in above-mentioned table 1,2.
○：More than 6 sections
△：3 sections less than 6 sections
×：Less than 3 sections
<The sensitivity after 6 months since the manufacture>
After manufacturing the 1st combination thing liquid and the 2nd combination thing liquid, 6 are preserved below 60% in 20~25 DEG C (room temperatures), humidity respectively
Mixed after individual month, sample is made in the same manner as the evaluation with above-mentioned sensitivity, is similarly evaluated.
<Resolution ratio>
The photosensitive polymer combination of each embodiment and comparative example is being formed into figuratum copper foil base using silk-screen printing
Whole face coating is carried out in a manner of dry film thickness turns into 10 μm on plate, 30 points are dried in 80 DEG C of hot-blast circulation dry furnace
Clock.After drying, by defined photomask (materials that 30 μm~100 μm of line), with ORC MANUFACTURING CO., LTD.
The metal halide lamp of system carries out 40mJ/cm2Exposure, with 30 DEG C of 1 mass % of spraying aqueous sodium carbonate 90 seconds, thus go
Except unexposed portion.After development, the state of the line residual of exposure portion is visually confirmed.Acquired results are shown in above-mentioned table 1,2.
○：Remain whole lines
△：The line of 40 μm~100 μm of residual
×：Non- residual wires
<The resolution ratio after 6 months since the manufacture>
After manufacturing the 1st combination thing liquid and the 2nd combination thing liquid, 6 are preserved below 60% in 20~25 DEG C (room temperatures), humidity respectively
Mixed after individual month, sample is made in the same manner as the evaluation with above-mentioned resolution ratio, is similarly evaluated.
<Elching resistant>
The photosensitive polymer combination of each embodiment and comparative example is being formed into figuratum copper foil base using silk-screen printing
Whole face coating is carried out in a manner of dry film thickness turns into 10 μm on plate, 30 points are dried in 80 DEG C of hot-blast circulation dry furnace
Clock.After drying, by defined photomask, 40mJ/cm is carried out with metal halide lamp2Exposure, with 30 DEG C spraying 1 mass %
Aqueous sodium carbonate 90 seconds, thus remove unexposed portion.Gained each sample is impregnated in chlorination copper etchant solution 10 minutes.
Each sample is taken out, after wiping etching solution, the stripping of the film of the exposure portion after development on visual valuation substrate.Metewand
It is as follows.Acquired results are shown in above-mentioned table 1,2.
○：The film of exposure portion is unstripped
×：The film of exposure portion is peeled off
Understood as shown in above-mentioned table, for containing gathering containing carboxy resin, oxime ester system Photoepolymerizationinitiater initiater, except oxime ester system light
Close photonasty tree of the Photoepolymerizationinitiater initiater and multifunctional (methyl) acrylate compounds beyond initiator as neccessary composition
Oil/fat composition, can highly have both elching resistant and sensitivity and resolution ratio, and developability, plyability are also excellent.
Claims (7)
1. a kind of photosensitive polymer combination, it is characterised in that contain：(A) trigger containing carboxy resin, the photopolymerization of (B) oxime ester system
Agent, the Photoepolymerizationinitiater initiater of (C) in addition to oxime ester system Photoepolymerizationinitiater initiater and (D) multifunctional (methyl) acrylate compounds.
2. photosensitive polymer combination according to claim 1, it is characterised in that (A) is not have containing carboxy resin
Have aromatic rings contains carboxy resin.
3. photosensitive polymer combination according to claim 1 or 2, it is characterised in that (C) removes the photopolymerization of oxime ester system
Photoepolymerizationinitiater initiater beyond initiator is acetophenone system Photoepolymerizationinitiater initiater.
4. according to photosensitive polymer combination according to any one of claims 1 to 3, it is characterised in that (D) is multifunctional
(methyl) acrylate compounds are multifunctional (methyl) acrylate compounds being modified through alkylene oxide.
5. according to photosensitive polymer combination according to any one of claims 1 to 4, it is characterised in that it is used to being formed anti-
Lose agent.
6. a kind of dry film, it is characterised in that it has photosensitive polymer combination according to any one of claims 1 to 5
The resin bed for being coated on film and making its drying to form.
7. a kind of manufacture method of printed circuit board (PCB), it is characterised in that possess following process：
Film formation process, photosensitive polymer combination is coated on to the surface of the conductor layer of the base material with conductor layer,
Form film；
Exposure process, to the film irradiation light, form the illumination part of intended shape；
Developing procedure, go unless illumination part and implement to pattern；
Etching work procedure, the conductor layer is implemented to etch using the film through the patterning as resist；With
Removing step, the film through the patterning is removed,
As the photosensitive polymer combination, the photosensitive polymer combination any one of usage right requirement 1~5.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-105546 | 2016-05-26 | ||
| JP2016105546 | 2016-05-26 | ||
| JP2017-024200 | 2017-02-13 | ||
| JP2017024200A JP2017215569A (en) | 2016-05-26 | 2017-02-13 | Photosensitive resin composition, dry film, and method for manufacturing printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107436536A true CN107436536A (en) | 2017-12-05 |
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| CN201710386503.0A Withdrawn CN107436536A (en) | 2016-05-26 | 2017-05-26 | The manufacture method of photosensitive polymer combination, dry film and printed circuit board (PCB) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019134528A1 (en) * | 2018-01-05 | 2019-07-11 | 湖北固润科技股份有限公司 | Photoresist composite using poly (p-hydroxystyrene)-containing epoxy resin as film-forming resin |
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2017
- 2017-05-26 CN CN201710386503.0A patent/CN107436536A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019134528A1 (en) * | 2018-01-05 | 2019-07-11 | 湖北固润科技股份有限公司 | Photoresist composite using poly (p-hydroxystyrene)-containing epoxy resin as film-forming resin |
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