CN108700805A - Photosensitive polymer combination, dry film, solidfied material, printed circuit board and Photobase generator - Google Patents
Photosensitive polymer combination, dry film, solidfied material, printed circuit board and Photobase generator Download PDFInfo
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- CN108700805A CN108700805A CN201780011878.7A CN201780011878A CN108700805A CN 108700805 A CN108700805 A CN 108700805A CN 201780011878 A CN201780011878 A CN 201780011878A CN 108700805 A CN108700805 A CN 108700805A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/56—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups bound to carbon atoms of six-membered aromatic rings and carboxyl groups bound to acyclic carbon atoms of the carbon skeleton
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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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
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
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- Materials Engineering (AREA)
- Materials For Photolithography (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
It provides:The excellent Photobase generator of the excellent photosensitive polymer combination of sensitivity, the dry film with the resin layer obtained by the composition, the solidfied material of resin layer of the composition or the dry film, the printed circuit board with the solidfied material, sensitivity.Photosensitive polymer combination etc., the photosensitive polymer combination is characterized in that, is contained:The Photobase generator for the ionic that carboxylic acid shown in the following general formula (1) is formed with alkali.(in formula (1), R1~R4,X1And X2It is each independently hydrogen atom or substituent group, X1And X2At least one of be electron-withdrawing group, Y is electron donating group, and B indicates alkali.).
Description
Technical field
The present invention relates to photosensitive polymer combination, dry film, solidfied material, printed circuit board and Photobase generators.
Background technology
The method that the Photobase generator that alkali is generated using the effect due to light makes resin chemical be modified as catalyst is applied to
The fields such as photo anti-corrosion agent material, photo-curing material.For example, a kind of photosensitive polymer combination has been recorded in patent document 1,
It is characterized in that, contains:Include the Photobase generator for the salt that the carboxylic acid for carrying out light decarboxylation is formed with tertiary amine;With, polyimide precursor and/
Or polybenzoxazole precursor.
Existing technical literature
Patent document
Patent document 1:No. 4830435 bulletins of Japan Patent
Invention content
Problems to be solved by the invention
It is required that improving the sensitivity of the photosensitive polymer combination containing Photobase generator.It, can be with if sensitivity improves
The reaction conditions such as the condition of heat treatment when mitigating condition that the light for generating alkali irradiates, carrying out heat cure using alkali, also phase
It waits for be patterned with good resolution ratio.In addition, if sensitivity improves, the selection of reaction condition as described above
Range is widened, other compositions, the base material etc. of photosensitive resin coating composition other materials in considering photosensitive polymer combination
The aspect of the characteristics such as the heat resistance of material expects that the reaction condition than being more suitable in the past can be selected.However, remembering in patent document 1
In the Photobase generator of the salt formed with tertiary amine comprising the carboxylic acid for carrying out light decarboxylation carried, it is unable to get sufficient sensitivity.
Therefore, the object of the present invention is to provide:The excellent photosensitive polymer combination of sensitivity has by the combination
Solidfied material, the printed circuit with the solidfied material of the resin layer of the dry film of the resin layer that object obtains, the composition or the dry film
The excellent Photobase generator of plate, sensitivity.
The solution to the problem
The inventors of the present invention have made intensive studies in view of above-mentioned, as a result, it has been found that:By that will have the compound of specific structure
It is used as Photobase generator, the above subject can be solved, so far complete the present invention.
That is, the photosensitive polymer combination of the present invention is characterized in that, contain:Carboxylic acid and alkali shown in the following general formula (1)
The Photobase generator of the ionic of formation.
(in formula (1), R1~R4,X1And X2It is each independently hydrogen atom or substituent group, X1And X2At least one of for inhale
Electron group, Y are electron donating group, and B indicates alkali.)
The photosensitive polymer combination of the present invention is preferably, and the molar absorption coefficient of aforementioned Photobase generator is 300L
mol-1·cm-1More than.
The photosensitive polymer combination of the present invention is preferably, and in aforementioned formula (1), electron-withdrawing group is selected from by-C ≡
N,-NO2,-COCH3,-F ,-Cl ,-Br and-I composition group.
The photosensitive polymer combination of the present invention is preferably, and in aforementioned formula (1), electron donating group is selected from by-CH3,-
C2H5,-CH(CH3)2,-C(CH3)3,-C6H5,-OH,-OCH3With-OC6H5The group of composition.
The photosensitive polymer combination of the present invention is preferably, and also contains macromolecule precursor.
The photosensitive polymer combination of the present invention is preferably, and aforementioned macromolecule precursor is polyamic acid and poly amic acid ester
In at least either.
The photosensitive polymer combination of the present invention is preferably, and aforementioned macromolecule precursor is with the following general formula (4-1) institute
The poly amic acid ester for the structure shown.
(in formula (4-1), R7For the organic group of 4 valences, R8For with alicyclic skeleton group, phenylene, with sub-
Any one of group and alkylidene of alkyl linked diphenylene skeleton, R9-1And R10-1It is optionally same or different to each other, is
The organic group of 1 valence or functional group with silicon, R11For the organic group of divalent, the integer that m is 1 or more, n is 0 or 1 or more
Integer.)
The photosensitive polymer combination of the present invention is preferably, the R in aforementioned formula (4-1)7For comprising aromatic ring with
The organic group of 4 valences of the fused rings of aliphatic hydrocarbon ring, 4 valences comprising aromatic group and alicyclic type hydrocarbon organic group,
Or the organic group of 4 valences comprising fluorine atom.
The photosensitive polymer combination of the present invention is preferably, and aforementioned macromolecule precursor is with the following general formula (4-1-1)
The poly amic acid ester of structure shown at least either in (4-1-2).
(in formula (4-1-1), R8For with alicyclic skeleton group, phenylene, with the two of alkylene sub- benzene
Any one of group and alkylidene of base skeleton, R9-1And R10-1Optionally be same or different to each other, be 1 valence organic group or
Functional group with silicon, R11For the organic group of divalent, the integer that m is 1 or more, the integer that n is 0 or 1 or more.)
(in formula (4-1-2), R8For with alicyclic skeleton group, phenylene, with the two of alkylene sub- benzene
Any one of group and alkylidene of base skeleton, R9-1And R10-1Optionally be same or different to each other, be 1 valence organic group or
Functional group with silicon, R11For the organic group of divalent, the integer that m is 1 or more, the integer that n is 0 or 1 or more.)
The dry film of the present invention is characterized in that thering is resin layer, the resin layer is by photosensitive resin combination
Obtained from being coated on film and drying.
The solidfied material of the present invention is characterized in that, is the resin layer by photosensitive resin combination or aforementioned dry film
Obtained from solidification.
The printed circuit board of the present invention is characterized in that thering is said curing object.
The Photobase generator of the present invention is characterized in that, is the ionic that carboxylic acid is formed with alkali shown in the following general formula (1).
(in formula (1), R1~R4,X1And X2It is each independently hydrogen atom or substituent group, X1And X2At least one of for inhale
Electron group, Y are electron donating group, and B indicates alkali.)
The Photobase generator of the present invention is preferably, and in aforementioned formula (1), electron-withdrawing group is-C ≡ N ,-COCH3,-NO2,-
F ,-Cl ,-Br and-I.
The Photobase generator of the present invention is preferably, and in aforementioned formula (1), electron donating group is-CH3,-C2H5,-CH
(CH3)2,-C(CH3)3,-C6H5,-OH,-OCH3With-OC6H5。
The effect of invention
According to the present invention it is possible to provide:The excellent photosensitive polymer combination of sensitivity, with what is obtained by the composition
The solidfied material of the resin layer of the dry film of resin layer, the composition or the dry film, the printed circuit board with the solidfied material, sensitivity
Excellent Photobase generator.
Description of the drawings
Fig. 1 is the Photobase generator MONPA-TBD for showing to synthesize in embodiment 1-11The figure of the spectrum of H-NMR.Horizontal axis table
Show that chemical shift (δ), the longitudinal axis indicate relative intensity (ppm).
Fig. 2 is the Photobase generator MONPA-DBU for showing to synthesize in embodiment 1-21The figure of the spectrum of H-NMR.Horizontal axis table
Show that chemical shift (δ), the longitudinal axis indicate relative intensity (ppm).
Fig. 3 is the Photobase generator MONPA-2E4MZ for showing to synthesize in embodiment 1-31The figure of the spectrum of H-NMR.Horizontal axis
Indicate that chemical shift (δ), the longitudinal axis indicate relative intensity (ppm).
Fig. 4 is the Photobase generator MONPA-DBA for showing to synthesize in embodiment 1-41The figure of the spectrum of H-NMR.Horizontal axis table
Show that chemical shift (δ), the longitudinal axis indicate relative intensity (ppm).
Specific implementation mode
Hereinafter, the ingredient contained to the photosensitive polymer combination of the present invention is described in detail.
[Guang Chanjianji ]
In the present invention, the Photobase generator for the ionic that carboxylic acid shown in the following general formula (1) and alkali are formed is used.
(in formula (1), R1~R4,X1And X2It is each independently hydrogen atom or substituent group, X1And X2At least one of for inhale
Electron group, Y are electron donating group, and B indicates alkali.Herein, substituent group refers to the group other than hydrogen atom.)
Aforementioned Photobase generator has the meta position in the phenyl ring from phenylacetic acid, and Direct Bonding has electron-withdrawing group respectively with contraposition
The structure of group and electron donating group.By such structure, alkali can be generated.
In addition, by above structure, under i rays (365nm) sensitivity also high Photobase generator can be manufactured.Aforementioned light
Molar absorption coefficient under the i rays of generated base alkaline agent is preferably 300Lmol-1·cm-1Above, it is more preferably 500Lmol-1·
cm-1Above, it is more preferably 1100Lmol-1·cm-1More than.Molar absorption coefficient is higher, has sensitivity to become higher
Tendency.The upper limit value of molar absorption coefficient is not particularly limited, from the viewpoint of photostability, storage stability, for example,
20000L·mol-1·cm-1Below.
In turn, the pyrolysis temperature (Td) of aforementioned Photobase generator is high, thus, for example thermal stability when dried coating film is also excellent
It is different.Preferably 120 DEG C or more, more preferable 150 DEG C or more, most preferably 180 DEG C or more of the Td of aforementioned Photobase generator.It needs to illustrate
It is that pyrolysis temperature (Td) refers to that weightless ratio becomes temperature when 10%.
As the active ray relative to aforementioned Photobase generator, luminous ray, ultraviolet light, electron beam, X-ray can be irradiated
Deng the preferred ultraviolet light of ultraviolet light, particularly 248nm, 365nm, 405nm, 436nm.
In aforementioned formula (1), R1,R2,X1And X2It is each independently hydrogen atom or substituent group.As substituent group, such as can
With enumerate halogen atom, hydroxyl, sulfydryl, sulfenyl, silicyl, silanol group, cyano, nitro, nitroso, sulfino, sulfo group,
Sulfonic acid foundation, phosphino-, phosphinyl, phosphate, phosphono, phosphonate group, alkoxy, amide groups or organic group.
Herein, organic group refers to including the group of carbon atom, and for example, carbon number is 10 groups below, can be had
Atom (such as hydrogen atom, oxygen atom, nitrogen-atoms, sulphur atom, halogen atom (fluorine atom, chlorine atom etc.) other than carbon atom
Deng).
X1And X2The electron-withdrawing group that may be used is not particularly limited, for example ,-C ≡ N ,-COCH3,-NO2,
With the halogen atoms such as-F ,-Cl ,-Br ,-I.In electron-withdrawing group, preferably-NO2.It should be noted that X1And X2In only one
In the case of electron-withdrawing group, another one is not particularly limited.
The electron donating group that Y may be used is not particularly limited, for example ,-CH3,-C2H5,-CH(CH3)2,-C
(CH3)3,-C6H5,-OH,-OCH3With-OC6H5.Wherein, preferably-OCH3。
R1And R2The substituent group that may be used is not particularly limited, for example, electron donating group.R1And R2It is preferred that dividing
It Wei not hydrogen atom.
R3And R4The substituent group that may be used is not particularly limited, for example, halogen atom, hydroxyl, sulfydryl, sulfenyl, first silicon
Alkyl, silanol group, cyano, nitro, nitroso, sulfino, sulfo group, sulfonic acid foundation, phosphino-, phosphinyl, phosphono, phosphonate ester
Base or organic group, can be the same or different.R3And R4It is preferred that being respectively hydrogen atom.
It should be noted that R1,R2,X1,X2Cyclic structure is not preferably formed with Y.
Alkali shown in B is not particularly limited, and the amine such as primary amine, secondary amine, tertiary amine (amine compounds), pyridine etc. can be used for example
Nitrogenous cyclic compound, hydrazine compound, amide compound, quaternary ammonium hydroxide etc..In addition, international publication number can be used for example
The alkali such as amine disclosed in WO2009/19979.In alkali, preferably secondary amine, tertiary amine, nitrogenous cyclic compound.Alkali shown in B is preferably strong
Alkali.
As alkali, for example,:Such, 1,4- Er Danzashuanhuans [ shown in following;2.2.2]Octane (DABCO),
N, N- dimethyl -4-aminopyridine (DMAP), 1- Dan Zashuanhuans [2.2.2]Bis- (dimethylamino) naphthalenes of octane (ABCO), 1,8-
(DMAN), diazabicyclo endecatylene (DBU), diazabicyclo-nonene (DBN), 1,1,3,3- tetramethylguanidine (TMG), 2- second
Base -4-methylimidazole (2E4MZ), piperidines (PPD), 1- ethyl-piperidins (EPPD), dibutyl amine (DBA), tri- azabicyclos of 1,5,7-
[4.4.0]- 5- decene (TBD) etc..
The pKa of aforementioned bases preferably 8~20, more preferable 10~16.
Aforementioned bases preferred DMAP, DMAN, DBU, TMG, 2E4MZ, PPD, EPPD, DBA and TBD.
Photobase generator shown in aforementioned preferred the following general formula of Photobase generator (2).
In formula (2), X1,X2, Y and B and formula (1) it is same.
In addition, Photobase generator shown in aforementioned more preferable the following general formula of Photobase generator (3).
In formula (3), B is same as formula (1).
Hereinafter, the concrete example as aforementioned Photobase generator, show with 4- methoxyl group -3- nitrophenyl-acetic acids (MONPA) and respectively
Photobase generator prepared by kind alkali, but it is not limited to these.
Aforementioned Photobase generator can be used singly or in combination of two or more.The compounding of aforementioned Photobase generator
Measure preferably 3~50 mass % in terms of photosensitive polymer combination total amount benchmark, more preferable 10~30 mass %.
The photosensitive polymer combination of the present invention can contain in the range of not impairing the effect of the present invention removes aforementioned light
Photobase generator other than generated base alkaline agent.
(macromolecule precursor)
In the photosensitive polymer combination of the present invention, changed as catalyst as using the alkali generated by aforementioned Photobase generator
The resin component of property, can contain macromolecule precursor.For macromolecule precursor, such as polyimide precursor, can enumerate
The macromolecule precursor of repetitive unit with polyamic acid or poly amic acid ester.
The macromolecule precursor of the aforementioned repetitive unit with polyamic acid or poly amic acid ester preferably uses the following general formula (4) table
Show.
In formula (4), R7For the organic group of 4 valences, R8For the organic group of divalent, R11For the organic group of divalent.As R11,
For example,:Including phenolic group, alkyl phenolic group, (methyl) are acrylate-based, cyclic alkyl, cyclic alkenyl radical, hydroxy amide acid
Base, aromatic series or aliphatic ester group, amide groups, amide imide base, carbonate group, siloxy group, alkylene oxide, carbamate
The group as constituent such as base, epoxy group, oxetanylmethoxy.Herein, organic group refers to including the group of carbon atom.
The integer that m is 1 or more, the integer that n is 0 or 1 or more.Herein, the preferred number-average molecular weight of macromolecule precursor is
1000~1,000,000, more preferable 5000~500,000 and then more preferable 10,000~200,000.
In formula (4), R7And R8According to purposes be selected from aromatic group, preferably the aromatic group of carbon atom number 6~32 or
The aliphatic group of aliphatic group, preferably carbon atom number 4~20.R7And R8Preferably used in the manufacture of macromolecule precursor
Substituent R contained in aftermentioned acid dianhydride and diamines7And R8。
In addition, in the case of photosensitive polymer combination is formed pattern by short-wavelength light, the absorption from polymer is special
From the perspective of property, as R7And R8, it is preferable to use aliphatic group.In addition, for example, using the group of fluorine is contained as R7With
R8In the case of, the low wavelength or dielectric property of light absorption can be improved.
In the present invention, the structure of macromolecule precursor is selected to be important according to purposes.
It should be noted that R74 valences indicate to be only used for and the sour valence mumber being bonded, R7There can be substituent group.Similarly,
R8Divalent indicate to be only used for the valence mumber that closes can further have substituent group in addition with amine key.
R9And R10For the organic group of hydrogen atom or 1 valence or with the functional group of silicon.
R9And R10In the case of organic group for 1 valence, for example, alkyl, alkenyl, alkynyl, aryl etc..R9With
R10In the case of the functional group with silicon for 1 valence, for example, siloxy group, silylation, silanol group etc..And
It can make R9And R10Only a part is hydrogen or the organic group of monovalence, thus, it is possible to control dissolubility.
As macromolecule precursor, it is suitble to use R9And R10For polyamic acid as hydrogen atom.Alkali-developable becomes good as a result,
It is good, good pattern can be obtained.
(polyamic acid)
Polyamic acid can be prepared by should be by by a conventionally known method.For example, can be only by by acid dianhydride and two
Amine is mixed and is prepared in the solution.It can be synthesized with the reaction of 1 step, can be easy and be obtained with low cost, without further
Modification, it is therefore preferable that using.The synthetic method of macromolecule precursor is not particularly limited, and can apply well known method.
As the example for the tetracarboxylic dianhydride that can be used in the present invention, tetrabasic carboxylic acid shown in the following general formula (5) can be enumerated
Dianhydride.But it is following shown in as an example of concrete example, without departing from the present invention purport just it is of course possible to using well known object
Matter.
(the R in formula7As noted above.)
It should be noted that the R in repetitive unit in the polyamic acid of present embodiment7Base is preferably originated from as polyamides
The R for the tetracarboxylic dianhydride that the raw material of amino acid manufacture uses7。
As the acid dianhydride that can be used to manufacture above-mentioned macromolecule precursor, for example,:1,3,3a, 4,5,9b- hexahydro-
5 (tetrahydrochysene -2,5- dioxo -3- furyls) Nai Bing [1,2-c]Furans -1,3- diketone, ethylidene tetracarboxylic dianhydride, butane tetracarboxylic
The aliphatic tetrabasic carboxylic acids two such as acid dianhydride, cyclobutane tetracarboxylic dianhydride, methyl cyclobutane tetracarboxylic dianhydride, pentamethylene tetracarboxylic dianhydride
Acid anhydride;Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides, 2,
3 ', 3,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides, 2,2 ', 3,3 '-biphenyltetracarboxylic dianhydrides,
Bis- (3,4- dicarboxyphenyis) propane of 2,3 ', 3,4 '-biphenyltetracarboxylic dianhydrides, 2,2 ', 6,6 '-biphenyltetracarboxylic dianhydrides, 2,2-
Bis- (2,3- dicarboxyphenyis) propane dianhydrides of dianhydride, 2,2-, bis- (3,4- dicarboxyphenyis) ether dianhydrides, bis- (3,4- dicarboxyl benzene
Base) sulfone dianhydride, bis- (2,3- dicarboxyphenyis) the ethane dianhydrides of 1,1-, bis- (2,3- dicarboxyphenyis) methane dianhydrides, bis- (3,4- bis-
Carboxyl phenyl) methane dianhydride, bis- (3,4- the dicarboxyphenyis) -1,1,1,3,3,3- hexafluoropropane dianhydrides of 2,2-, the bis- (2,3- of 2,2-
Dicarboxyphenyi) -1,1,1,3,3,3- hexafluoropropane dianhydrides, bis- ((3,4- dicarboxyls) benzoyl) benzene dianhydrides of 1,3-, 1,4-
Bis- { 4- (4- (1,2- dicarboxyls) phenoxy group) phenyl } propane dianhydrides of bis- ((3,4- dicarboxyls) benzoyl) benzene dianhydrides, 2,2-,
Bis- { 4- (3- (1,2- dicarboxyls) phenoxy group) phenyl } propane dianhydrides of 2,2-, bis- { 4- (4- (1,2- dicarboxyls) phenoxy group) phenyl }
Ketone dianhydride, bis- { 4- (3- (1,2- dicarboxyls) phenoxy group) phenyl } ketone dianhydrides, 4,4 '-bis- (4- (1,2- dicarboxyls) phenoxy groups) connection
Benzene dianhydride, 4,4 '-bis- (3- (1,2- dicarboxyls) phenoxy group) biphenyl dianhydrides, bis- { 4- (4- (1,2- dicarboxyls) phenoxy group) phenyl }
Ketone dianhydride, bis- { 4- (3- (1,2- dicarboxyls) phenoxy group) phenyl } ketone dianhydrides, bis- { 4- (4- (1,2- dicarboxyls) phenoxy group) benzene
Base } sulfone dianhydride, bis- { 4- (3- (1,2- dicarboxyls) phenoxy group) phenyl } sulfone dianhydrides, bis- { 4- (4- (1,2- dicarboxyls) phenoxy group)
Phenyl } thioether dianhydride, bis- { 4- (3- (1,2- dicarboxyls) phenoxy group) phenyl } thioether dianhydrides, bis- { 4- (4- (the 1,2- dicarboxyls of 2,2-
Base) phenoxy group) phenyl -1,1,1,3,3,3- hexafluoropropane dianhydrides, bis- { 4- (3- (1,2- dicarboxyls) phenoxy group) benzene of 2,2-
Base } -1,1,1,3,3,3- hexafluoropropane dianhydrides, 2,3,6,7- naphthalene tetracarboxylic acids dianhydride, 1,1,1,3,3,3- hexafluoros -2,2- it is bis- (2,
3- or 3,4- dicarboxyphenyis) propane dianhydride, 1,4,5,8- naphthalene tetracarboxylic acids dianhydride, 1,2,5,6- naphthalene tetracarboxylic acids dianhydride, 1,2,3,
4- benzene tertacarbonic acids dianhydride, 3,4,9,10- tetracarboxylic dianhydrides, 2,3,6,7- anthracenes tetracarboxylic dianhydride, 1,2,7,8- phenanthrene tetrabasic carboxylic acid two
Acid anhydride, pyridine tetracarboxylic dianhydride, sulfonyl diphthalic anhydrides, meta-terphenyl base -3,3 ', 4,4 '-tetracarboxylic dianhydrides, to three
Phenyl -3,3 ', aromatic tetracarboxylic acids' dianhydride such as 4,4 '-tetracarboxylic dianhydrides etc..
They can be used alone or mix two or more use.Moreover, as the tetracarboxylic dianhydride particularly preferably used,
1,3,3a, 4,5,9b- hexahydros -5 (tetrahydrochysene -2,5- dioxo -3- furyls) Nai Bing [ can be enumerated;1,2-c]Furans -1,3- two
Ketone, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides, 2,2 ', 6,
6 '-biphenyltetracarboxylic dianhydrides, bis- (3,4- dicarboxyphenyis) ether dianhydrides, 2,2- bis- (3,4- dicarboxyphenyis) -1,1,1,3,3,
3- hexafluoropropane dianhydrides.
It, can be with using when having imported the acid dianhydride of fluorine, the acid dianhydride with alicyclic ring skeleton as the acid dianhydride being applied in combination
In the case where less destroying the transparency, the physical property such as adjustment dissolubility, coefficient of thermal expansion.In addition, using pyromellitic dianhydride, 3,
3 ', 4,4 '-biphenyltetracarboxylic dianhydrides, Isosorbide-5-Nitrae, when the acid dianhydride of the rigidity such as 5,8- naphthalene tetracarboxylic acid dianhydrides, finally obtained polyamides is sub-
The coefficient of linear thermal expansion of amine becomes smaller, but has the tendency that the transparency is interfered to improve, and therefore, the copolymerization ratios side combination that can be anticipated with marginal not makes
With.
Multiple carboxyls of acid dianhydride can reside on single aromatic rings, can also exist on multiple aromatic rings, example
As acid dianhydride shown in following formula can be used.
The amine that can be used in the present invention can enumerate diamines shown in the following general formula (6).But following is an example, as long as
Without prejudice to the purport of the present invention, just it is of course possible to using well known diamines.
H2N-R8-NH2 (6)
(the R in formula8As noted above.)
As R8The example of diamines when base is the aromatic group of divalent, can enumerate p-phenylenediamine, 3,3 '-dimethyl-
4,4 '-benzidines, 2,2 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 3,
Bis- (4- aminophenyls) anthracenes of 3 '-two chloro- 4,4 '-benzidines, 9,10-, 4,4 '-diaminobenzophenones, 4,4 '-diamino
It is bis- (3- amino-benzene oxygens) benzene of diphenyl sulfone, 3,3 '-diamino diphenyl sulfones, 4,4 '-diaminodiphenyl sulfoxides, 1,3-, double
(4- (4- amino-benzene oxygens) phenyl) sulfone, bis- (4- (3- amino-benzene oxygens) phenyl) sulfones, 4,4 '-bis- (4- amino-benzene oxygens) connection
Benzene, 4,4 '-bis- (3- amino-benzene oxygens) biphenyl, bis- (4- (4- amino-benzene oxygens) phenyl) ethers, 1,1,1,3,3,3- hexafluoros -2,2-
Bis- (4- aminophenyls) propane, 1,1,1,3,3,3- hexafluoros -2,2- it is bis- (4- (4- amino-benzene oxygens) phenyl propane, 1,1,1,3,
Bis- (3- amino -4- aminomethyl phenyls) propane of 3,3- hexafluoros -2,2-, m-phenylene diamine (MPD), 4,4 '-diamino-diphenyl ethers, 4,4 '-diaminos
Bis- (4- amino-benzene oxygens) benzene of base diphenylsulfide, 3,4 '-diamino-diphenyl ethers, 1,4-, 1,3- bis- (4- amino-benzene oxygens)
Benzene.
As R8The example of diamines when base is the aliphatic group of divalent, can enumerate 1,1- m-xylene diamines, 1,3- third
Diamines, tetra-methylenedimine, five methylene diamine, hexamethylene diamine, heptamethylene diamines, eight methylene diamines, nine methylenes
Base diamines, 4,4- diamino heptamethylenes diamines, 1,4- diaminocyclohexanes, isophorone diamine, tetrahydrochysene dicyclopentadienyl
Diamines, hexahydro -4,7- methyl Asia indanyl dimethylene diamines, San Huan [6.2.1.02,7]Hendecene dimethyl-p-phenylenediamine, 4,
4 '-di-2-ethylhexylphosphine oxides (cyclohexylamine), isophorone diamine.
In addition, as another example, diamino polysiloxane etc. shown in the following general formula (11) can be enumerated.
Wherein, in formula, R28And R29Each independently represent the alkyl of divalent, R30And R31Each independently represent monovalence
Alkyl.The integer that p is 1 or more, preferably 1~10.
Specifically, as the R in above-mentioned formula (11)28And R29, the carbon numbers such as methylene, ethylidene, propylidene can be enumerated
The arlydene etc. of the carbon numbers such as 1~7 alkylidene, phenylene 6~18, as R30And R31, the carbon numbers such as methyl, ethyl 1 can be enumerated
The aryl etc. of the carbon numbers such as~7 alkyl, phenyl 6~12.
It, can also be suitable for using poly amic acid ester in addition, as macromolecule precursor.Poly amic acid ester can be by well known
Method obtains.
For example, making 3, the acid anhydrides such as 3 '-benzophenone tetracarboxylic dianhydrides react to form half ester with alcohol such as ethyl alcohol.Use protochloride
Sulfone makes the half ester form diester diacid chloride.Make the diester diacid chloride and 3, the diamine reactants such as 5- diaminobenzoic acids, to obtain
The ester of polyamic acid.
In photosensitive polymer combination, as the repetitive unit with polyamic acid or poly amic acid ester at least part
Macromolecule precursor, can use single kind material, can also as a mixture use it is a variety of.Alternatively, it is also possible to
For R7And R8In at least either formed respectively by multiple structures, copolymer.
In addition, the diisocyanate such as half ester and isophorone diisocyanate obtained from making above-mentioned acid anhydrides be reacted with alcohol are anti-
It answers, so as to obtain poly amic acid ester.It should be noted that compared with the synthetic method for using above-mentioned diamines, it is different using two
The synthetic method of cyanate can easily synthesizing polyamides acid esters.
As the diisocyanate that can be used to obtain poly amic acid ester, two isocyanides shown in the following general formula (7) can be enumerated
Acid esters.But it is following as an example of, without departing from the present invention purport, so that it may to use well known diisocyanate.
OCN-R8-NCO (7)
(the R in formula8As noted above.)
As aforementioned diisocyanates, isophorone diisocyanate (ITI), toluene di-isocyanate(TDI) can be enumerated
(TDI), bis- (4- isocyanatophenyis) hexafluoropropane of 4,4 '-diisocyanate methylene diphenyl esters (MDI), 2,2-, six methylenes
Group diisocyanate (HMDI) etc..
Aforementioned macromolecule precursor is preferably the poly amic acid ester with structure shown in the following general formula (4-1).
(in formula (4-1), in the same manner as aforementioned formula (4), R7For the organic group of 4 valences, R8For the organic group of divalent, R11
For the organic group of divalent, the integer that m is 1 or more, the integer that n is 0 or 1 or more.R9-1And R10-1Optionally it is same or different to each other,
Organic group for 1 valence or the functional group with silicon.R8Group, phenylene preferably with alicyclic skeleton, with sub-
Any one of group and alkylidene of alkyl linked diphenylene skeleton.)
In formula (4-1), R7Shown in the organic groups of 4 valences be not particularly limited, selected according to purposes.Such as it can
To enumerate:The aromatic group or aliphatic group of aromatic group, preferably carbon atom number 6~32, preferably carbon atom number 4~
20 aliphatic group.R7In acid dianhydride shown in the aforementioned formula (5) used in the manufacture of preferably aforementioned macromolecule precursor
Contained substituent R7。
For the poly amic acid ester with structure shown in aforementioned formula (4-1), from the viewpoint of resolution ratio, R7Especially
Preferably include the organic group of aromatic ring and 4 valences of the fused rings of aliphatic hydrocarbon ring, include aromatic group and ester ring type
The organic group of the organic group of 4 valences of alkyl or 4 valences comprising fluorine atom.
The organic group of aforementioned 4 valences comprising fluorine atom preferably have aromatic group (preferably phenyl, naphthalene, particularly
Phenyl), preferably there is trifluoromethyl and aromatic group.
Poly amic acid ester with structure shown in aforementioned formula (4-1) is preferably with the following general formula (4-1-1) and (4-1-
2) structure shown in at least either in.
(in formula (4-1-1), R8,R9-1,R10-1,R11, m and n and formula (4-1) it is same.)
(in formula (4-1-2), R8,R9-1,R10-1,R11, m and n and formula (4-1) it is same.)
R in formula (4-1)8Group, phenylene preferably with alicyclic skeleton, with the two of alkylene sub-
Any one of group and alkylidene of phenyl skeleton.Aforementioned phenylene and alkylidene respectively in formula (4-1) with R8The 2 of bonding
A nitrogen-atoms Direct Bonding.On the other hand, aforementioned alicyclic skeleton and the aforementioned diphenylene skeleton with alkylene can be with
With in formula (4-1) with R82 nitrogen-atoms Direct Bondings of bonding, can not also be bonded.R8The system of preferably aforementioned macromolecule precursor
Make substituent R contained in diisocyanate shown in diamines or aforementioned formula (7) shown in the aforementioned formula (6) used8。
R8In the aforementioned group with alicyclic skeleton can also form fused rings with substituent group.Aforementioned tool
There is the group of alicyclic skeleton preferably the following general formula (8A) to be used to indicate.
(in formula (8A), n1 indicates 0~10 integer, R8A1For aliphatic group, preferably indicate carbon number 1~5 alkylidene,
More preferably indicate methylene, R8A2It is separately aliphatic group or aromatic group, preferably indicates the fat such as methyl, ethyl
Fat race group.)
R8In aforementioned phenylene can have substituent group, fused rings can also be formed.Aforementioned phenylene is preferably with following
General formula (8B) indicates.
(in formula (8B), n2 indicates 0~4 integer, R8B1It is separately aliphatic group or aromatic group, preferably
Indicate the aliphatic groups such as methyl, ethyl.)
R8In it is aforementioned with can be with substituent group with the group of the diphenylene skeleton of alkylene, can also shape
At fused rings.It is aforementioned that there is the group with the diphenylene skeleton of alkylene preferably with the following general formula (8C) expression.
(in formula (8C), n3 and n4 separately indicate 0~4 integer, R8C1And R8C2It is separately fatty group
Group or aromatic group preferably indicate the aliphatic groups such as methyl, ethyl, R8C3Indicate the alkylidene of carbon number 1~5.)
R in formula (8C)8C3Alkylidene can have the substituent groups such as aliphatic group or aromatic group.
R8In the alkylidene of the preferred carbon number of aforementioned alkylidene 1~10, more preferable carbon number 2~8 alkylidene.It needs to illustrate
, R8In aforementioned alkylidene can have the substituent groups such as aliphatic group or aromatic group.
For excellent in resolution, R8It is preferred that the group with alicyclic skeleton, more preferably has alicyclic skeleton and does not have
There is the group of aromatic backbone.
In the present invention, the R in formula (4-1)9-1And R10-1It is separately the organic group of 1 valence or the function with silicon
Group.As R9-1And R10-1In aforementioned 1 valence organic group, for example, alkyl, alkenyl, alkynyl, aryl etc..As
R9-1And R10-1In aforementioned 1 valence the functional group with silicon, for example, siloxy group, silylation, silanol group etc..
Dissolubility when the synthesis of poly amic acid ester, the R in formula (4-1)9-1And R10-1Optimizing alkyl.
As alkyl, for example, methyl, ethyl, propyl, butyl, amyl, hexyl etc..Herein the preferred butyl of alkyl, amyl or
Hexyl.
In the present invention, the R in formula (4-1)11For the organic group of divalent, for example, including aromatic series or aliphatic
The base that ester group, amide groups, amide imide base, siloxy group, epoxy group, oxetanylmethoxy etc. are constituted as at least part
Group.
Hereinafter, being illustrated to the other compositions that can be compounded in the photosensitive polymer combination of the present invention.
As long as in the photosensitive polymer combination of the present invention solvent that can use can make Photobase generator, macromolecule precursor and
The dissolving of other additives is just not particularly limited.As an example, N, N '-dimethyl formamide, N- crassitudes can be enumerated
Ketone, N- ethyl-2-pyrrolidones, N, N '-dimethyl acetamide, diethylene glycol dimethyl ether, cyclopentanone, gamma-butyrolacton, α-acetyl
Base-gamma-butyrolacton, tetramethylurea, 1,3- dimethyl -2- imidazolines, n-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), pregnancy
Base phosphamide, pyridine, gamma-butyrolacton, diethylene glycol monomethyl ether.They can be used alone, can also by two or more mix and
It uses.The amount of the solvent used is not particularly limited, for example, according to coating film thickness, viscosity and relative to 100 matter of macromolecule precursor
Part is measured with the range use of 50~9000 mass parts.
In order to further increase luminous sensitivity, sensitizer can also be added in the photosensitive polymer combination of the present invention.
As sensitizer, for example, Michler's keton, 4,4 '-bis- (diethylamino) benzophenone, bis- (the 4 '-diethyl aminos of 2,5-
Base benzal) pentamethylene, bis- (the 4 '-diethylamino benzal) cyclohexanone of 2,6-, bis- (the 4 '-dimethylamino benzal of 2,6-
Base) -4- methyl cyclohexanones, bis- (4 '-diethylamino the benzal) -4- methyl cyclohexanones of 2,6-, 4,4 '-bis- (dimethylaminos)
Chalcone, 4,4 '-bis- (diethylamino) chalcone pitch dimethylamino Chinese cassia tree base indone, to dimethylamino benzal
Base indone, 2- (to dimethylaminophenyl biphenylene)-benzothiazole, 2- (to dimethylaminophenyl ethenylidene) benzene
And thiazole, 2- (to dimethylaminophenyl ethenylidene) different aphthothiazoles, 1,3- bis- (4 '-dimethylamino benzals) third
Bis- (the 4 '-diethylamino benzal) acetone of ketone, 1,3-, 3,3 '-carbonyls-bis- (7- diethyl amino coumarins), 3- acetyl group-
7- dimethylaminos butylcoumariii, 3- ethoxy carbonyl -7- dimethylaminos butylcoumariii, 3- benzyloxycarbonyl -7- dimethylaminos
Cumarin, 3- methoxycarbonyl -7- diethyl amino coumarins, 3- ethoxy carbonyl -7- diethyl amino coumarins, N- benzene
Base-N '-ehtylethanolamine, N- phenyldiethanol-amines, N- p-methylphenyls diethanol amine, N- phenylethanol amines, 4- morpholinyl hexichol
Ketone, dimethylaminobenzoic acid isopentyl ester, diethylamino isoamyl benzoate, 2-mercaptobenzimidazole, 1- phenyl -5- mercaptos
Base tetrazolium, 2-mercaptobenzothiazole, 2- are (to dimethylaminostyryl) benzoxazoles, 2- (to dimethylaminostyrene
Base) benzothiazole, 2- (to dimethylaminostyryl) naphtho- (1,2-d) thiazole, 2- (to dimethvlaminobenzovl)
Styrene etc., from sensitivity aspect, it is preferable to use the thioxanthene ketone class such as 4- (1- Methylethyls) -9H- thioxanthene-9-ones.It
Can be used alone or be applied in combination with 2~5 kinds.It is preferable to use 0.1 relative to 100 mass parts of macromolecule precursor for sensitizer
~10 mass parts.
In addition, in order to improve the cementability with base material, bonding can also be compounded in photosensitive polymer combination of the invention
Auxiliary agent.As bonding additives, well known bonding additives can be used without departing from the purport of the present invention.For example,
Gamma-amino propyldimethoxy-silane, N- (beta-aminoethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane, γ-epoxy third
Oxygroup hydroxypropyl methyl dimethoxysilane, γ-mercapto propyl methyl dimethoxy silane, N-[3- (triethoxysilyl)
Bing Ji ]The reaction product etc. of phthalyl amino acid, benzophenone tetracarboxylic dianhydride and (triethoxysilyl) propylamine.It is viscous
Connect range of the compounding amount of auxiliary agent relative to 100 mass parts of macromolecule precursor preferably 0.5~10 mass parts.
In addition, in the photosensitive polymer combination of the present invention, base-proliferating agent can also be added.When forming the pattern of thick film,
The resolution ratio of the Photobase generator of same degree is required from a surface to lower section.At this point, in order to improve sensitivity, alkali proliferation is preferably added
Agent.It can be used for example disclosed in Japanese Unexamined Patent Publication 2012-237776 bulletins, Japanese Unexamined Patent Publication 2006-282657 bulletins etc.
Base-proliferating agent.
It should be noted that in the range of the membrane property after not destroying solidification substantially, in the photoresist of the present invention
Other photonasty ingredients that acid is generated by light can be added in composition.Add in the photosensitive polymer combination of the present invention
When entering that there is 1 or 2 or more the compound of ethylenic unsaturated bond, optical free radical producing agent can be added.
In order to assign processing characteristics, various functions to the photosensitive polymer combination of the present invention, can be compounded in addition each
The low molecule or high-molecular compound of kind organic or inorganic.Can be used for example dyestuff, surfactant, levelling agent, plasticizer,
Particle etc..Include the nothings such as organic fine particles, colloidal silicon dioxide, carbon, the phyllosilicates such as polystyrene, polytetrafluoroethylene (PTFE) in particle
Machine particle etc., they can be Porous, hollow structure.As the specific material for obtaining Porous shape, hollow structure
Material, there is various pigment, filler and fiber etc..
It is by being coated with the present invention in carrier film (supporter) that the dry film of the present invention, which has resin layer, the resin layer,
Photosensitive polymer combination and obtained from drying.The formation of dry film is as follows:The photosensitive polymer combination of the present invention is used
Organic solvent diluting is stated, viscosity appropriate is adjusted to, then uses comma coater, knife type coater, lip coating machine, rod coating
Machine, extrusion press, inverse formula coating machine, transmission roll-coater, gravure coater, flush coater etc. are applied with uniform thickness on a carrier film
Cloth.Later, the photosensitive polymer combination of coating is usually carried out at a temperature of 50~130 DEG C to drying in 1~30 minute, to
Resin layer can be formed.For coating film thickness, be not particularly limited, generally with after drying film thickness gauge, 10~150 μm, it is excellent
Suitable for selection in the range of selecting 20~60 μm.
As carrier film, using plastic film, it is preferable to use the polyester films such as polyethylene terephthalate, polyamides are sub-
The plastic films such as amine film, polyamidoimide film, polypropylene film, polystyrene film.For the thickness of carrier film, do not have
There is special limitation, generally suitable for selection in the range of 10~150 μm.
After forming the resin layer of the photosensitive polymer combination comprising the present invention on a carrier film, adhere to for dust is prevented
In the surface of film the purpose of, in turn, the protective film that can be removed preferably is laminated on the surface of film.As the protective film that can be removed, example
Polyethylene film, polytetrafluoroethylene film, polypropylene film, surface treated paper can such as be used.It, will as protective film
When protecting film stripping, as long as less than the bonding force of resin layer and carrier film.
Then, the manufacturing method about the pattern film of the solidfied material as the photosensitive polymer combination for using the present invention,
As an example, it is illustrated as the case where macromolecule precursor for compounding polyimide precursor, that is, poly amic acid ester.
First, as step 1, photosensitive polymer combination is coated on base material and is dried, to obtain film.As
Photosensitive polymer combination is coated on the method on base material, can use and be used in the coating of previous photosensitive polymer combination
Method, such as the method being coated with spin coater, bar coater, knife type coater, curtain coater, screen process press;
The method for carrying out spraying coating with flush coater;And ink-jet method etc..As the drying means of film, air-dried using utilization, baking oven
Or hot plate heat drying, vacuum drying the methods of.In addition, the dry of film it is expected in not causing photosensitive polymer combination
Poly amic acid ester imidizate under conditions of carry out.Specifically, can at 20~140 DEG C, with 1 minute~1 hour
Condition spontaneously dried, dry or heat drying of blowing.It is preferred that carrying out drying in 1~20 minute on hot plate.In addition,
It can be dried in vacuo, at this point it is possible to carry out at room temperature, with 1 minute~1 hour condition.
Base material is not particularly limited, Silicon Wafer, circuit board, various resins, metal, semiconductor dress are can be widely applied to
The passivation protection film etc. set.
In addition, which is characterized in that since the imidizate under low temperature can be carried out, printed circuit board can be widely used in
Substrate etc. is unsuitable for the component of high-temperature process, material.
Then, as step 2, above-mentioned film is exposed by the figuratum photomask of tool or is directly exposed.
Exposure light generates the light of the wavelength of alkali using Photobase generator can be made to activate.It, can be with when suitable for using sensitizer as above-mentioned
Adjust luminous sensitivity.As exposure device, contact aligner, mirror projection, stepping exposure device, laser direct imaging can be used
Exposure device etc..
Then, it as step 3, is heated in the way of promoting the imidizate of film by the alkali generated in film.
The alkali generated as a result, in exposure portion in above-mentioned steps 2 becomes catalyst, poly amic acid ester partly imidizate.Heating time
With heating temperature according to use poly amic acid ester, coating film thickness, the type of Photobase generator and suitable for change.Typically, 10 μm
It it is 2~10 minutes or so at 110~200 DEG C in the case of the coating film thickness of left and right.It, can not be effective when heating temperature is too low
Reach the imidizate of part in ground.On the other hand, when heating temperature is excessively high, the imidizate in unexposed portion carries out, and can reduce exposure
The deliquescent difference in light portion and unexposed portion has and forms the worry counteracted to pattern.
Then, as step 4, film is handled with developer solution.Thus, it is possible to which it includes polyamide to be formed on base material
The pattern film of the polyimides of acid esters and partly imidizate.
It, can be from the developing method of previously known photoresist, such as rotation spray as the method used in development
Coating, paddle method, with selecting arbitrary method in infusion process of ultrasonication etc..As developer solution, hydroxide can be enumerated
The organic amines such as the inorganic bases such as sodium, sodium carbonate, sodium metasilicate, ammonium hydroxide, ethamine, diethylamine, triethylamine, triethanolamine, tetramethyl
The aqueous solution of the quaternary ammonium salts such as ammonium hydroxide, tetrabutylammonium hydroxide etc..In addition, as needed, can be added in them suitable
The water-miscible organic solvents such as methanol, ethyl alcohol, the isopropanol of equivalent, surfactant form aqueous solution and use.Later, according to need
Film is cleaned using flushing liquor to obtain pattern film.As flushing liquor, it can be used alone or be applied in combination:Distillation
Water, methanol, ethyl alcohol, isopropanol etc..
In addition, as developer solution, n-methyl-2-pyrrolidone, N- acetyl group -2-Pyrrolidone, N can be used for example,
Dinethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, hexamethylphosphoramide, methanol, second
Alcohol, isopropanol, methyl carbitol, ethyl carbitol, toluene, dimethylbenzene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether
Acetic acid esters, methyl -3- methoxy propyls acid esters, ethyl -3- ethoxy-cs acid esters, 2-HEPTANONE, ethyl acetate, diacetone alcohol etc. are organic
Solvent.
Later, as step 5, pattern film is heated.Heating temperature is cured can make the pattern film of polyimides
Mode is suitable for setting.For example, the heating for carrying out 5~120 minutes or so in non-active gas, with 150~300 DEG C.Heating temperature
The ranging from 150~250 DEG C preferred of degree, further preferred range are 180~220 DEG C.Heating is for example by using heat
Plate, baking oven, can set temperature program temperature lifting type baking oven and carry out.As atmosphere (gas) at this time, air can be used,
The non-active gas such as nitrogen, argon gas can be used.
The purposes of photosensitive polymer combination of the present invention is not particularly limited, for example, printer's ink, bonding agent,
Filler, electronic material, photoelectricity circuit unit, moulding material, anticorrosive additive material, construction material, three-dimensional appearance, optical component etc. make
Various field products etc. well known to resin material.Especially it is suitable as heat resistance, the dimensionally stable of polyimide film
Extensive field/product, such as coating or the printer's ink or colour filter, Flexible Displays that the characteristics such as property, insulating properties are considered valid
Device film, semiconductor element device, electronic unit, interlayer dielectric, solder mask etc. connect up cover film, optical circuit, optical circuit
The forming material of component, antireflection film, holographic, optical component or construction material.
In particular, in the case of containing polyimide precursor as macromolecule precursor, photosensitive resin composition of the invention
Object is used mainly as pattern forming material (resist), and the pattern film being consequently formed is sent out as the permanent film comprising polyimides
The effect as the ingredient for assigning heat resistance, insulating properties is waved, for example, suitably forming colour filter, flexible display film, electronics
Component, semiconductor device, interlayer dielectric, solder mask, cover film etc. connect up cover film, Xi Di, optical circuit, photoelectricity circuit unit,
Antireflection film, other optical components or electronic component.
In the present invention, carboxylic acid shown in the following general formula (8) can be mixed with alkali and be manufactured by aforementioned generated base alkaline agent.
4- methoxies shown in carboxylic acid, further preferred following formula (10) shown in more preferable the following general formula of aforementioned carboxylic acid (9)
Base -3- nitrophenyl-acetic acids (MONPA).
In formula (8), (9), R1~R4,X1,X2, Y and aforementioned formula (1) it is same.
As aforementioned bases, alkali shown in B in aforementioned formula (1) can be used.
The mixing of aforementioned carboxylic acid and alkali is preferably protected from light and the solution of alkali is added dropwise in the solution of carboxylic acid and carries out.
Embodiment
Hereinafter, the present invention is illustrated in more details using embodiment, but the present invention is not limited to the following examples.It needs
It is noted that " part " and " % " all quality criterias unless otherwise specified in following.
[The He Cheng ] of carboxylic acid;
(refer to synthesis example 1:The synthesis of 4- methoxyl group -3- nitrophenyl-acetic acids (MONPA))
In bis- mouthfuls of eggplant type bottles of 500ml, in 0 DEG C, by concentrated nitric acid (67 mass %) 30ml and 4- methoxyphenylacetic acids
(MOPA) 3.32g (20.0mmol) is mixed, and is stirred (room temperature, 6h).Mixture obtained by being added dropwise in cold water after being filtered, is used
Cold water wash obtains 4- methoxyl group -3- nitrophenyl-acetic acids (MONPA) (yield as flaxen solids:2.51g, receive
Rate:60%).
[The He Cheng ] of Photobase generator;
(embodiment 1-1:The synthesis of MOMPA-TBD)
In 50ml eggplant type bottles, by the 4- methoxyl group -3- nitrobenzenes of the drying ethanol for being dissolved in 10ml synthesized among the above
Acetic acid (MONPA) 0.300g (1.42mmol) and be dissolved in 10ml dry ethyl alcohol tri- Dan Zashuanhuan [ of 1,5,7-;4.4.0]-5-
Decene (TBD) 0.198g (1.42mmol) is mixed, and a Dinner is stirred at room temperature.Gained mixture is concentrated, EtOH/Et is used2O is again
Precipitation, obtains the MOMPA-TBD (yield as orange viscous liquid:0.289g, yield:58%).It will1H-NMR
(300MHz,CDCl3) be illustrated in Fig. 1, in addition, the analysis result at peak is shown in following.
δ 1.96 (quint, J=5.9Hz, 4H ,-CH2-),3.1-3.4(m,8H,-NCH2-),3.53(s,2H,Bn-H),
3.92(s,3H,-OCH3), 7.00 (d, J=8.6Hz, 1H, Ar-H), 7.51 (dd, J=8.6,2.2Hz, 1H, Ar-H), 7.85
(d, J=2.2Hz, 1H, Ar-H), 10.64 (br, 1.4H, NH)
(embodiment 1-2:The synthesis of MOMPA-DBU)
By the tri- Dan Zashuanhuan [ of 1,5,7- in synthesis example 1;4.4.0]- 5- decene (TBD) 0.198g (1.42mmol) changes
It in addition to this with method identical with synthesis example 1, is obtained for diazabicyclo endecatylene (DBU) 0.216g (1.42mmol)
MOMPA-DBU (yield as orange viscous liquid:0.419g, yield:81%).It will1H-NMR(300MHz,CDCl3)
It is illustrated in Fig. 2, in addition, the analysis result at peak is shown in following.
δ1.6-1.8(m,6.7H,-CH2), 1.99 (quint, J=6.0Hz, 2H ,-CH2-),2.7-2.9(m,2H,-
CH2-),3.3-3.5(m,6H,-NCH2-),3.56(s,2H,Bn-H),3.92(s,3H,-OCH3), 6.99 (d, J=8.6Hz,
1H, Ar-H), 7.53 (dd, J=8.6,2.2Hz, 1H, Ar-H), 7.86 (d, J=2.2Hz, 1H, Ar-H)
(embodiment 1-3:The synthesis of MOMPA-2E4MZ)
By the tri- Dan Zashuanhuan [ of 1,5,7- in synthesis example 1;4.4.0]- 5- decene (TBD) 0.198g (1.42mmol) changes
It in addition to this with method identical with synthesis example 1, is obtained for 2-ethyl-4-methylimidazole (2E4MZ) 0.156g (1.42mmol)
To the MOMPA-2E4MZ (yield as orange viscous liquid:0.186g, yield:41%).It will1H-NMR(300MHz,
CDCl3) be illustrated in Fig. 3, in addition, the analysis result at peak is shown in following.
δ 1.12 (t, J=7.6Hz, 6H ,-CH2CH3),2.15(s,3H,-CH3), 2.65 (q, J=7.6Hz, 2H ,-
CH2CH3),3.61(s,2H,Bn-H),3.93(s,3H,-OCH3), 6.56 (s, 1H, Im-H), 7.01 (d, J=8.6Hz, 1H,
), Ar-H 7.48 (dd, J=8.6,2.2Hz, 1H, Ar-H), 7.82 (d, J=2.2Hz, 1H, Ar-H)
(embodiment 1-4:The synthesis of MOMPA-DBA)
By the tri- Dan Zashuanhuan [ of 1,5,7- in synthesis example 1;4.4.0]- 5- decene (TBD) 0.198g (1.42mmol) changes
It in addition to this with method identical with synthesis example 1, obtains consolidating as orange for dibutyl amine (DBA) 0.184g (1.42mmol)
MOMPA-DBA (the yield of body object:0.473g, yield:98%).It will1H-NMR(300MHz,CDCl3) be illustrated in Fig. 4, in addition,
The analysis result at peak is shown in following.
δ 0.86 (t, J=7.3Hz, 6H ,-CH3), 1.26 (sext, J=7.3Hz, 4H ,-CH2-),1.4-1.6(m,4H,-
CH2-),2.6-2.7(m,4H,-CH2-),3.47(s,2H,Bn-H),3.93(s,3H,-OCH3), 6.99 (d, J=8.6Hz, 1H,
), Ar-H 7.44 (dd, J=8.6,2.2Hz, 1H, Ar-H), 7.81 (d, J=2.2Hz, 1H, Ar-H)
(comparative example 1-1:The synthesis of Photobase generator described in Japanese Patent No. 4830435)
By Ketoprofen 5.09g (20mmol) and 1,4- Er Danzashuanhuans [2.2.2]Octane 1.12g (10mmol) inputs are burnt
Bottle, is heated at 50 DEG C, slowly puts into hexamethylene until Ketoprofen and Isosorbide-5-Nitrae-Er Danzashuanhuan [2.2.2]Octane is completely dissolved.
Later, when cooling, the precipitation of white is obtained.At 45 DEG C be dried under reduced pressure within 2 hours, obtain it is following shown in Photobase generator.
[The ] of the molar absorption coefficient of Photobase generator;
Each Photobase generator synthesized among the above is surveyed using Shimadzu Scisakusho Ltd MultiSpec-1500
Determine UV-vis spectrum, measures the molar absorption coefficient under i rays (365nm).Solution cuvette uses quartz system and optical path length 1cm
Cuvette.It should be noted that molar absorption coefficient is mole of the absorbance of solution divided by the thickness of absorbed layer and solute
It is worth obtained from concentration.Show the result in table 1.
[Table 1]
It is found that meeting the molar absorption coefficient under the i rays of the Photobase generator of embodiment 1-1~1-4 of aforementioned formula (1)
It is high.
[The Ping Jia ] of the heat resistance of Photobase generator;
For the Photobase generator (MONPA-TBD) of embodiment 1-1, using Mac Science corporation TG-DTA2000S,
Carry out TG-DTA measurement (5 DEG C/min of heating rate), it is thus identified that until 200 DEG C are nearby stablized.
[The He Cheng ] of poly amic acid ester;
(synthesis example 1:The synthesis of poly amic acid ester A-1)
Dry tertiary fourth is added in as the 6FDA of acid dianhydride (4,4 '-(hexafluoroisopropyli,ene base) diphthalic anhydrides) 5g
Alcohol about 25g simultaneously flows back.Reflux obtains the liquid of substantially transparent in about 30 minutes after starting.In turn, it flows back about 5 hours, it is cooling, use hole
The filter that 0.7 μm of diameter is filtered removal impurity.It is dried under reduced pressure, the tert-butyl alcohol is completely removed, obtained in the form of white crystal
To the half ester of acid anhydrides recorded in table 1.
The half ester 5mmol of acid anhydrides recorded in table 1 and anhydrous 3- methyl-1s-are put into the three-necked flask of capacity 100ml
After phenyl -2- Phospholes 1- oxides 0.0125mmol, side flows into nitrogen, while being dissolved with the dehydration sulfolane of 10ml.Make
Anhydrous ITI (isophorone diisocyanate) 5mmol 5ml as diisocyanate were dehydrated sulfolane dissolving, with about 5 minutes
It is added dropwise in flask.So that mixed solution is reacted with 200 DEG C, 3 hours, is precipitated with MeOH 500ml.By the solution mistake comprising precipitation
Filter, is dried, obtains macromolecule precursor polymer.Resulting polymers are dissolved in DMAc (n,N-dimethylacetamide), are used
MeOH reprecipitations.It is filtered, dries, to be dehydrated DMAc as solvent, make the poly amic acid ester A-1 solution of 15 mass %.
[Table 2]
(synthesis example 2:The synthesis of poly amic acid ester A-2)
As acid dianhydride, 6FDA is changed to TDA (- 5 (tetrahydrochysene -2,5- dioxo -3- furans of 1,3,3a, 4,5,9b- hexahydro
Mutter base) Nai Bing [1,2-c]Furans -1,3- diketone), in addition to this, poly amic acid ester A-2 solution is made in the same manner as synthesis example 1.
[Table 3]
(synthesis example 3:The synthesis of poly amic acid ester A-3)
By 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride (ODPA) 7.75g and 4,4 '-diamino-diphenyls ethers (DDE)
4.86g is dissolved in N-Methyl pyrrolidone (NMP) 30g, is stirred 4 hours at 60 DEG C, a Dinner is stirred at room temperature later, obtains
Polyamic acid.Thereto, under water cooling, trifluoroacetic anhydride 9.45g is added, is stirred at room temperature 3 hours, ethyl alcohol 1.73g is added.
The reaction solution is added dropwise in distilled water, filters and collects sediment, be dried under reduced pressure, to make poly amic acid ester A-3's
Solution.The number-average molecular weight of poly amic acid ester A-3 is 27000.
(embodiment 2-1)
With the mix ratio (mass ratio) described in following tables, the solution relative to the poly amic acid ester obtained among the above is compounded
Photobase generator simultaneously dissolves, and obtains the photosensitive polymer combination of embodiment and comparative example.It should be noted that the polyamide in table
The compounding amount of acid esters indicates solid content.
The photosensitive polymer combination of the embodiment 2-1 in following tables is coated on 4 inches of Silicon Wafer by being spin-coated on,
It is heated 20 minutes on 80 DEG C of hot plate, forms the photosensitive polymer combination film of 10 μm of thickness.For the film, it is equipped with i and penetrates
The high-pressure sodium lamp exposure device of line optical filter, by mask pattern, with 0~1000mJ/cm2The light quantity of range be exposed.
After exposure, heats 10 minutes on 140 DEG C of hot plate, then, be impregnated in weight ratio 1:1 is mixed with tetramethylammonium hydroxide
The developer solution of 2.38% aqueous solution and 2- propyl alcohol 90 seconds, and then wash 20 seconds, to carry out pattern development.
As a result, can be confirmed through the amount of being exposed 150mJ/cm2Above light irradiates to form pattern.
(embodiment 2-2~2-9, comparative example 2-1~2-3)
By the step same as embodiment 2-1, with described in following tables mix ratio (mass ratio) and light exposure implement
Development experiment confirms the light exposure that pattern is formed.
[Table 4]
*1:In 1000mJ/cm2Under can not also carry out pattern and formed.
It is found that the sensitivity of the photosensitive polymer combination of the embodiment containing the Photobase generator for meeting aforementioned formula (1)
It is excellent, although for the condition of cure of low temperature, patternability is excellent.
Claims (15)
1. a kind of photosensitive polymer combination, which is characterized in that contain:Carboxylic acid shown in the following general formula (1) and alkali formed from
The Photobase generator of subtype,
In formula (1), R1~R4,X1And X2It is each independently hydrogen atom or substituent group, X1And X2At least one of be electrophilic
Group, Y are electron donating group, and B indicates alkali.
2. photosensitive polymer combination according to claim 1, which is characterized in that the molar absorptivity system of the Photobase generator
Number is 300Lmol-1·cm-1More than.
3. photosensitive polymer combination according to claim 1, which is characterized in that in the general formula (1), electron-withdrawing group
Selected from by-C ≡ N ,-COCH3,-NO2,-F ,-Cl ,-Br and-I composition group.
4. photosensitive polymer combination according to claim 1, which is characterized in that in the general formula (1), electron donating group
Selected from by-CH3,-C2H5,-CH(CH3)2,-C(CH3)3,-C6H5,-OH,-OCH3With-OC6H5The group of composition.
5. photosensitive polymer combination according to claim 1, which is characterized in that also contain macromolecule precursor.
6. photosensitive polymer combination according to claim 5, which is characterized in that the macromolecule precursor is polyamic acid
With at least either in poly amic acid ester.
7. photosensitive polymer combination according to claim 5, which is characterized in that the macromolecule precursor is with following
The poly amic acid ester of structure shown in general formula (4-1),
In formula (4-1), R7For the organic group of 4 valences, R8For with alicyclic skeleton group, phenylene, with using alkylene bond
Any one of group and alkylidene of the diphenylene skeleton of conjunction, R9-1And R10-1It is optionally same or different to each other, is 1 valence
Organic group or functional group with silicon, R11For the organic group of divalent, the integer that m is 1 or more, the integer that n is 0 or 1 or more.
8. photosensitive polymer combination according to claim 7, which is characterized in that the R in the general formula (4-1)7For comprising
The organic groups of 4 valences of the fused rings of aromatic ring and aliphatic hydrocarbon ring, 4 valences comprising aromatic group and alicyclic type hydrocarbon
The organic group of organic group or 4 valences comprising fluorine atom.
9. photosensitive polymer combination according to claim 5, which is characterized in that the macromolecule precursor is with following
The poly amic acid ester of structure shown at least either in general formula (4-1-1) and (4-1-2),
In formula (4-1-1), R8For with alicyclic skeleton group, phenylene, with the diphenylene skeleton with alkylene
Group and any one of alkylidene, R9-1And R10-1It is optionally same or different to each other, for the organic group of 1 valence or with silicon
Functional group, R11For the organic group of divalent, the integer that m is 1 or more, the integer that n is 0 or 1 or more,
In formula (4-1-2), R8For with alicyclic skeleton group, phenylene, with the diphenylene skeleton with alkylene
Group and any one of alkylidene, R9-1And R10-1It is optionally same or different to each other, for the organic group of 1 valence or with silicon
Functional group, R11For the organic group of divalent, the integer that m is 1 or more, the integer that n is 0 or 1 or more.
10. a kind of dry film, which is characterized in that there is resin layer, the resin layer is by photoresist described in claim 1
Obtained from composition is coated on film and dries.
11. a kind of solidfied material, which is characterized in that it is by photosensitive polymer combination according to any one of claims 1 to 9
Or obtained from the resin layer solidification of dry film according to any one of claims 10.
12. a kind of printed circuit board, which is characterized in that with the solidfied material described in claim 11.
13. a kind of Photobase generator, which is characterized in that it is the ionic that carboxylic acid is formed with alkali shown in the following general formula (1),
In formula (1), R1~R4,X1And X2It is each independently hydrogen atom or substituent group, X1And X2At least one of be electrophilic
Group, Y are electron donating group, R1~R4It is each independently hydrogen atom or substituent group, B indicates alkali.
14. Photobase generator according to claim 13, which is characterized in that in the general formula (1), electron-withdrawing group is selected from
By-C ≡ N ,-COCH3,-NO2,-F ,-Cl ,-Br and-I composition group.
15. the Photobase generator according to claim 13 or 14, which is characterized in that in the general formula (1), electron donating group choosing
Freely-CH3,-C2H5,-CH(CH3)2,-C(CH3)3,-C6H5,-OH,-OCH3With-OC6H5The group of composition.
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| PCT/JP2017/004015 WO2017141734A1 (en) | 2016-02-16 | 2017-02-03 | Photosensitive resin composition, dry film, cured product, printed circuit board, and photobase generator |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3499008A (en) * | 1964-04-29 | 1970-03-03 | Nobel Bozel | Butyl ester of bis(glycidyloxy-4-phenyl) acetic acid |
| JP2007101685A (en) * | 2005-09-30 | 2007-04-19 | Dainippon Printing Co Ltd | Photosensitive resin composition and article |
| CN101970572A (en) * | 2007-08-09 | 2011-02-09 | 积水化学工业株式会社 | Photocurable composition |
| JP2011080032A (en) * | 2009-09-08 | 2011-04-21 | Tokyo Univ Of Science | New compound, base generating agent, and photosensitive resin composition containing the base generating agent |
| JP2011133699A (en) * | 2009-12-25 | 2011-07-07 | Jsr Corp | Radiation sensitive resin composition, interlayer dielectric and method for forming the same |
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| US5206117A (en) * | 1991-08-14 | 1993-04-27 | Labadie Jeffrey W | Photosensitive polyamic alkyl ester composition and process for its use |
| WO2008115572A1 (en) * | 2007-03-21 | 2008-09-25 | Theraquest Biosciences, Inc. | Methods and compositions of nsaids |
| JP5120029B2 (en) * | 2008-03-31 | 2013-01-16 | 大日本印刷株式会社 | Photosensitive resin composition, article using the same, and negative pattern forming method |
| JP5321188B2 (en) * | 2008-03-31 | 2013-10-23 | 大日本印刷株式会社 | Photosensitive resin composition, article, and pattern forming method |
| JP5997041B2 (en) * | 2012-12-26 | 2016-09-21 | 東京応化工業株式会社 | Photosensitive resin composition |
| KR101869619B1 (en) * | 2013-12-04 | 2018-06-20 | 산아프로 가부시키가이샤 | Photobase generator |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3499008A (en) * | 1964-04-29 | 1970-03-03 | Nobel Bozel | Butyl ester of bis(glycidyloxy-4-phenyl) acetic acid |
| JP2007101685A (en) * | 2005-09-30 | 2007-04-19 | Dainippon Printing Co Ltd | Photosensitive resin composition and article |
| CN101970572A (en) * | 2007-08-09 | 2011-02-09 | 积水化学工业株式会社 | Photocurable composition |
| JP2011080032A (en) * | 2009-09-08 | 2011-04-21 | Tokyo Univ Of Science | New compound, base generating agent, and photosensitive resin composition containing the base generating agent |
| JP2011133699A (en) * | 2009-12-25 | 2011-07-07 | Jsr Corp | Radiation sensitive resin composition, interlayer dielectric and method for forming the same |
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| KR20180107270A (en) | 2018-10-01 |
| TW201800845A (en) | 2018-01-01 |
| JP6767470B2 (en) | 2020-10-14 |
| TWI720127B (en) | 2021-03-01 |
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