CN109324481A - Photosensitive polymer combination, dry film, solidfied material, printed circuit board and semiconductor element - Google Patents
Photosensitive polymer combination, dry film, solidfied material, printed circuit board and semiconductor element Download PDFInfo
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- CN109324481A CN109324481A CN201810843721.7A CN201810843721A CN109324481A CN 109324481 A CN109324481 A CN 109324481A CN 201810843721 A CN201810843721 A CN 201810843721A CN 109324481 A CN109324481 A CN 109324481A
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
There is provided carried out thick light-sensitive surface (for example, 5 μm or more) on plated substrate developability is especially excellent and resolution ratio is also excellent, solidfied material, the printed circuit board and semiconductor element with the solidfied material of the resin layer of the good photosensitive polymer combination of pattern form after development, the dry film with the resin layer obtained by the composition, the composition or the dry film.A kind of photosensitive polymer combination, using its dry film, solidfied material, printed circuit board and semiconductor element, the photosensitive polymer combination contains: at least any one in (A) polybenzoxazoles precursor, (B) emulsion, (C) mercaptan compound and (D) urea compounds and melamine based compound.
Description
Technical field
The present invention relates to photosensitive polymer combination, dry film, solidfied material, printed circuit board and semiconductor elements.
Background technique
As the photosensitive polymer combination that can develop in alkaline aqueous solution, using by polybenzoxazoles (hereinafter, also referred to as
For composition made of the compounding of " the PBO ") photoacid generators such as precursor and diazo naphthoquinone compound.This composition heat cured is obtained
The heat resistance and electrical insulating property of the polybenzoxazoles solidfied material arrived are excellent therefore exhausted in the surface protection film of electric material, interlayer
In velum, the electronic component such as the film of semiconductor element, flexible printed circuit board material, high temperature insulation interlayer materials
Using being in progress.
About the photosensitive polymer combination for having used polybenzoxazoles, for example, being covered in patent document 1 for obstruction copper
The purpose of the formation of residue (hereinafter also referred to as " dross ") after development on lid wafer, discloses before polybenzoxazoles
Compounding includes photosensitive polymer combination made of the pyrimidine scaffold compound of S atom in body polymer.In addition, patent document 2
In, to provide the photosensitive polymer composition of high sensitivity, the shape of pattern, the residual film ratio also good eurymeric in unexposed portion
For the purpose of, disclose the technology containing following substance: selected from defined poly amic acid ester, with diamines and tetracarboxylic acid with phenolic hydroxyl group
Acid, its acid anhydride or derivatives thereof are polyimides obtained from raw material, using dicarboxylic acids and dihydroxy diamine to gather obtained from raw material
The polymer of alkaline aqueous solution solubility in benzoxazoles precursor；Diazido o-quinone (o-quinone diazide) chemical combination
Object；And the dissolution Inhibitors in salt, biaryl compound and tetraalkylammonium salt.
Existing technical literature
Patent document
Patent document 1: No. 4759613 bulletins of Japanese Patent No.
Patent document 2: No. 3509612 bulletins of Japanese Patent No.
Summary of the invention
Problems to be solved by the invention
However, according to technology disclosed in Patent Document 1, although can obtain being coated with to by positive type photosensitive organic compound
In the obstruction effect of the formation of dross on copper covering wafer and when film obtained from roasting is exposed/develops, after development
Fruit, but due to can also obtain dissolution facilitation effect, the dissolution in unexposed portion is too fast sometimes, so that the pattern after development is cut
Face shape is rounded and carefully, and residual film ratio is also low, generates adverse effect to next thin copper film formation process.In addition, according to patent
Technology disclosed in document 2, although being obtained to positive type photosensitive organic compound is coated on silicon substrate and is dried
To film be exposed/develop when, the residual film ratio after development can be improved, but the Metal Substrate due to there is above-mentioned gained film
The obstruction effect of dissolution on plate, therefore the removal of the film of exposure portion is insufficient, can remain a large amount of drosses on metallic substrates.
In turn, the technology of the pattern form on silicon substrate is controlled although it is known that through addition plasticizer, crosslinking agent etc., in gold
Belonging to cannot get good effect on substrate.
Therefore, the object of the present invention is to provide carrying out the thick light-sensitive surface on plated substrate (for example, 5
μm or more) developability is especially excellent and resolution ratio is also excellent, the good photosensitive resin composition of pattern form after development
Object, the dry film with the resin layer obtained by the composition, the composition or the dry film resin layer solidfied material, consolidate with this
The printed circuit board and semiconductor element of compound.
The solution to the problem
The inventors of the present invention have made intensive studies, as a result, it has been found that, by being compounded mercaptan compound and compounding urine to PBO precursor
At least any one in plain compound and melamine based compound, can solve the above problems, so as to complete the present invention.
That is, photosensitive polymer combination of the invention is characterized in that, contain: (A) polybenzoxazoles precursor, (B) are photosensitive
At least any one in agent, (C) mercaptan compound and (D) urea compounds and melamine based compound.
Dry film of the invention is characterized in that having and photosensitive resin combination is coated on film and is dried
Obtained from resin layer.
Solidfied material of the invention is characterized in that, by the resin layer shape of photosensitive resin combination or aforementioned dry film
At.
Printed circuit board and semiconductor element of the invention is characterized in that thering is said curing object.
The effect of invention
The aobvious of the thick light-sensitive surface on plated substrate (for example, 5 μm or more) has been carried out in accordance with the invention it is possible to provide
Shadow is especially excellent and resolution ratio is also excellent, the good photosensitive polymer combination of pattern form after development, has by this
The solidfied material of the resin layer of the dry film of the resin layer that composition obtains, the composition or the dry film, the printing with the solidfied material
Circuit board and semiconductor element.
Detailed description of the invention
Fig. 1 is the explanatory diagram of the evaluation method of the pattern form in embodiment.
Fig. 2 be embodiment 4 using contact pin type surface-profile measuring instrument Dektak, (Bruker corporation, contact pin type are imitative
Shape system, hereinafter also referred to as " Dektak ") obtained cross section profile data.
Fig. 3 is the cross section profile data of comparative example 1 obtained using Dektak.
Fig. 4 is the cross section profile data of comparative example 2 obtained using Dektak.
Specific embodiment
Hereinafter, embodiments of the present invention will be described in detail.
Photosensitive polymer combination of the invention contains: (A) polybenzoxazoles precursor, (B) emulsion, (C) mercaptan chemical combination
At least any one in object and (D) urea compounds and melamine based compound.By adding to photonasty PBO combination of precursors
Add (D) for being easy that effect is hindered with (C) mercaptan compound of metal interaction and with dissolution due to isolated electron pair
At least any one in urea compounds and melamine based compound can obtain resolution ratio to inhibit the generation of dross
The good photonasty of developability that is excellent, particularly having carried out the thick light-sensitive surface (for example, 5 μm or more) on plated substrate
Resin combination.Using photosensitive polymer combination of the invention, what the cross sectional shape of line image after development will not become
Thin and circle is able to maintain that cross sectional shape is the good pattern form of cone-shaped (trapezoidal shape or quadrilateral shape).
Firstly, each ingredient that photosensitive polymer combination of the invention contains is described in detail.
[(A) polybenzoxazoles precursor]
Photosensitive polymer combination of the invention contains (A) polybenzoxazoles precursor.Synthesize (A) polybenzoxazoles precursor
Method is not particularly limited, and is synthesized by well known method.For example, can make dihydroxy diamine class as amine component with
The two carboxylic acid halides reaction of the dicarboxylic acids such as the dicarboxyl diacid chloride as sour component obtains.
(A) polybenzoxazoles precursor is preferably the polyhydroxyamide acid with repetitive structure shown in following formula (1).
(in formula, X indicates that the organic group of 4 valences, Y indicate the organic group of divalent.The integer that n is 1 or more, preferably 10~
50,20~40 are more preferably.)
In the case where synthesizing (A) polybenzoxazoles precursor by above-mentioned synthetic method, in aforementioned formula (1), X is aforementioned
The residue of dihydroxy diamine class, Y are the residue of foregoing dicarboxylic acids.
As aforementioned dihydroxy diamine class, 3,3 '-diamino -4,4 '-dihydroxybiphenyls, 4,4 '-diamino-can be enumerated
3,3 '-dihydroxybiphenyls, bis- (3- amino-4-hydroxylphenyl) propane, bis- (4- amino-3-hydroxy base) propane, bis- (3- ammonia
Base -4- hydroxy phenyl) sulfone, bis- (4- amino-3-hydroxy base) sulfones, bis- (the 3- amino-4-hydroxylphenyls) -1,1,1,3,3 of 2,2-,
Bis- (4- amino-3-hydroxy base) -1,1,1,3,3,3- hexafluoropropane of 3- hexafluoropropane, 2,2- etc..Wherein, preferably 2,2- is bis-
(3- amino-4-hydroxylphenyl) -1,1,1,3,3,3- hexafluoropropane.
As foregoing dicarboxylic acids, M-phthalic acid, terephthalic acid (TPA), 5- tert-butyl isophthalic acid, 5- bromine can be enumerated
M-phthalic acid, 5- fluorine M-phthalic acid, 5- chlorine M-phthalic acid, 2,6 naphthalene dicarboxylic acid, 4,4 '-dicarboxylate biphenyls, 4,4 '-two
Carboxyl diphenyl ether, 4,4 '-dicarboxyl tetraphenyl silane, bis- (4- carboxyl phenyl) sulfones, bis- (to the carboxyl phenyl) propane of 2,2-, 2,
Bis- (4- carboxyl phenyl) -1,1,1,3,3,3- hexafluoropropane of 2- etc. have the dicarboxylic acids of aromatic rings, oxalic acid, malonic acid, succinic acid,
The fatty families dicarboxylic acids such as 1,2- cyclobutane dicarboxylic acid, 1,4- cyclohexane dicarboxylic acid, 1,3- cyclopentane dicarboxylic acid.Wherein, preferably
4,4 '-dicarboxydiphenyl ethers.
In aforementioned formula (1), the organic group for 4 valences that X is indicated can be aliphatic group, or aromatic series base
Group, preferably aromatic group, more preferable 2 hydroxyls and 2 amino are located on aromatic rings in a manner of ortho position.Aforementioned 4 valence
The carbon atom number of aromatic group is preferably 6~30, more preferably 6~24.Aromatic group as aforementioned 4 valence it is specific
Example, can enumerate following radicals, but be not limited to these, and may include in selection polybenzoxazoles precursor depending on the application is well known
Aromatic group.
It is preferably following radicals in aforementioned fragrance race group for the aromatic group of aforementioned 4 valence.
In aforementioned formula (1), the organic group for the divalent that Y is indicated can be aliphatic group, or aromatic series base
Group, preferably aromatic group, more preferably on aromatic rings with the carbonyl linkage in aforementioned formula (1).The aromatic series of aforementioned divalent
The carbon atom number of group is preferably 6~30, more preferably 6~24.The concrete example of aromatic group as aforementioned divalent can arrange
Following radicals are enumerated, but are not limited to these, select well known aromatic series base contained in polybenzoxazoles precursor depending on the application
Group.
(in formula, A is indicated selected from by singly-bound ,-CH2-、-O-、-CO-、-S-、-SO2-、-NHCO-、-C(CF3)2-、-C
(CH3)2The group of divalent in the group of composition.)
It is preferably following radicals in aforementioned fragrance race group for the organic group of aforementioned divalent.
(A) polybenzoxazoles precursor may include the repetitive structure of above-mentioned polyhydroxyamide acid of more than two kinds.In addition, also
It may include the structure in addition to the repetitive structure of above-mentioned polyhydroxyamide acid, for example, may include the repetition knot of polyamic acid
Structure.
(A) number-average molecular weight (Mn) of polybenzoxazoles precursor be preferably 5000~100000, more preferably 8000~
50000.Herein, number-average molecular weight is numerical value obtained from being measured as GPC and being converted with standard polystyren.Separately
Outside, the matter average molecular weight (Mw) of (A) polybenzoxazoles precursor be preferably 10000~200000, more preferably 16000~
100000.Herein, matter average molecular weight is numerical value obtained from being measured as GPC and being converted with standard polystyren.
Mw/Mn is preferably 1~5, more preferably 1~3.
(A) polybenzoxazoles precursor can be used singly or in combination of two or more.(A) polybenzoxazoles
The compounding amount of precursor is preferably 30~95 mass %, more preferably 50~90 matter in terms of composition solid ingredient total amount benchmark
Measure %.
[(B) emulsion]
It as (B) emulsion, is not particularly limited, photoacid generator, Photoepolymerizationinitiater initiater, Photobase generator can be used.Light
Acid agent is the compound that acid can be generated by the light irradiation of ultraviolet light, visible light etc., and Photoepolymerizationinitiater initiater is by same
Light irradiation can generate free radicals equal compound, Photobase generator for by same light irradiate molecular structure change or
Person's molecular cleavage and the compound for generating a kind or more alkaline matter.In the present invention, as (B) emulsion, it can be suitably used
Photoacid generator.
As photoacid generator, diazo naphthoquinone compound, diaryl sulfonium salt, triarylsulfonium salt, dialkyl benzene first can be enumerated
Acyl Methylsulfonium Salt, diaryl iodonium salt, aryl diazonium salts, aromatic tetracarboxylic acid's ester, aromatic sulfonic acid ester, p-Nitrobenzyl, fragrance
Race N- oxygen acid imide sulphonic acid ester, aromatic sulfonamide, benzoquinones diazosulfonic acid ester etc..Photoacid generator preferably dissolves Inhibitors.Its
In preferably diazo naphthoquinone compound.
As diazo naphthoquinone compound, three (4- hydroxy phenyl) -1- ethyl -4- isopropyls specifically can be used for example
The diazo naphthoquinone addition product (for example, TS533, TS567, TS583, TS593 of Triratna chemistry institute Co. Ltd. system) of benzene, four
Dihydroxy benaophenonel diazo naphthoquinone addition product (for example, BS550, BS570 of Triratna chemistry institute Co. Ltd. system,
BS599), the diazo naphthoquinone addition product (example of 4- { 4- [bis- (4- hydroxy phenyl) ethyls of 1,1-]-bis (alpha, alpha-dimethylbenzyl) base } phenol
Such as, TKF-428, TKF-528 of Triratna chemistry institute Co. Ltd. system) etc..
In addition, usual well known Photoepolymerizationinitiater initiater can be used, it is, for example, possible to use tools as Photoepolymerizationinitiater initiater
There are the oxime ester system Photoepolymerizationinitiater initiater, alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, the photopolymerization of acylphosphine oxide system of oxime ester base to draw
Send out agent, luxuriant titanium system Photoepolymerizationinitiater initiater etc..
The CGI- of BASF JAPAN LTD. can be enumerated as commercially available product as aforementioned oxime ester system Photoepolymerizationinitiater initiater
325, N-1919, NCI-831 etc. of IRGACURE OXE01, IRGACURE OXE02, ADEKA CORPORATION.
As aforementioned alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, specifically, 2- methyl-1-[4- (methyl can be enumerated
It is thio) phenyl] -2- morpholinyl -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl) -1- butanone, 2- (two
Methylamino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] -1- butanone, N, N- dimethylamino benzene second
IRGACURE 907, the IRGACURE 369, IRGACURE of BASF JAPAN LTD. can be used as commercially available product in ketone etc.
379 etc..
As aforementioned acylphosphine oxide system Photoepolymerizationinitiater initiater, specifically, 2,4,6- trimethylbenzoyls can be enumerated
Base diphenyl phosphine oxide, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, bis- (2,6- Dimethoxybenzoyls)-
2,4,4- trimethyl-pentyl phosphine oxides etc., as commercially available product, can be used BASF JAPAN LTD. IRGACURE TPO,
The Omnirad 819 etc. of IGM Resins corporation.
As aforementioned luxuriant titanium system Photoepolymerizationinitiater initiater, specifically, bis- (cyclopentadienyl group) diphenyl titaniums, double can be enumerated
(cyclopentadienyl group) titanium chloride, bis- (cyclopentadienyl groups)-bis- (2,3,4,5,6- pentafluorophenyl group) titaniums, bis- (cyclopentadienyl groups)-
Bis- (the fluoro- 3- of 2,6- bis- (pyrroles -1- base) phenyl) titaniums etc..As commercially available product, it can enumerate BASF JAPAN LTD.'s
IRGACURE 784 etc..
In addition, can be ionic Photobase generator, or non-ionic Photobase generator, ion as Photobase generator
High sensitivity of the type Photobase generator due to composition, the formation to pattern film are advantageous, preferably.As alkaline matter, such as
Secondary amine, tertiary amine can be enumerated.
As the Photobase generator of ionic, salt and the light that carboxylic acid and tertiary amine containing aromatic component can be used for example are pure
WPBG-082, WPBG-167, WPBG-168, WPBG-266, WPBG-300 etc. of medicine Co. Ltd. system ionic PBG.
As non-ionic Photobase generator, such as alpha-aminoacetophenone compound can be enumerated, oxime ester compound, had
N- formylation aromatic series amino, N- are acylated aromatic series amino, nitrobenzylamino formic acid ester group, alkoxybenzyl amino first
The compound etc. of the substituent groups such as perester radical.As other Photobase generators, WPBG-018 (trade name: 9- can be used
Anthrylmethyl N, N '-diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2-
Hydroxyphenyl) -2-propenoyl] piperidine), WPBG-140 (trade name: 1- (anthraquinon-2-yl)
Ethyl imidazolecarboxylate), WPBG-165 etc..
(B) emulsion can be used singly or in combination of two or more.(B) compounding amount of emulsion is with group
Closing object solid component total amount benchmark meter is preferably 0.5~40 mass %, more preferably 1~30 mass %.
[(C) mercaptan compound]
As (C) mercaptan compound, be not particularly limited, can be used D, L- dithiothreitol (DTT), 2 mercapto ethanol and
Compound shown below etc..Especially wherein preferred D, L- dithiothreitol (DTT).
(C) mercaptan compound can be used singly or in combination of two or more.(C) mercaptan compound is matched
Mixed amount is preferably 0.01~20 mass %, more preferably 0.1~10 mass % in terms of composition solid ingredient total amount benchmark.Pass through
It is set as above range, so as to more reliably inhibit the generation of dross.
[in (D) urea compounds and melamine based compound at least any one]
(D1) urea compounds and (D2) trimerization are contained as (D) ingredient for photosensitive polymer combination of the invention
At least any one in cyanamide based compound.Urea compounds and melamine based compound can respectively be used alone, can also
To be applied in combination.
It as (D1) urea compounds, is not particularly limited, the bis- [4- (three of 1,3- diphenyl urea, 1,3- can be used for example
Methyl fluoride) phenyl] urea, N, bis- (trimethyl silyl) ureas of N ' -, 1- acetyl group -3- methylurea, 1- acetyl group -2- thiocarbamide, second
Uride, 1- adamantyl thiocarbamide, 1- allyl -3- (2- hydroxyethyl) -2- thiocarbamide, benzoylene urea, N- benzoyl sulphur
Bis- (4- chlorphenyl) ureas of bis- (tert-butoxycarbonyl) thiocarbamides of urea, benzoyl urea, benzylurea, 1,3-, 1,3-, bis- (the 4- fluorobenzene of 1,3-
Base) urea, 1,3- (hydroxymethyl) urea, bis- (4- methoxyphenyl) ureas of 1,3-, biruea, Butylurea, N, N '-diethyl-N, N '-
Diphenyl urea etc..
(D1) urea compounds can be used singly or in combination of two or more.(D1) urea compounds
Compounding amount is preferably 0.01~15 mass %, more preferably 0.05~10 mass % in terms of composition solid ingredient total amount benchmark.
By being set as above range, to improve residual film ratio, the developability of thick light-sensitive surface on metallic substrates is improved, can developed
After obtain more good pattern form.
In addition, the ratio as (C) mercaptan compound and (D1) urea compounds, preferably (C) mercaptan compound are (D1)
It is more than the equivalent of urea compounds.Especially in terms of quality criteria, compounding amount/(D1) urea compounds of (C) mercaptan compound
Compounding amount ratio be preferably 1:1~10:1, more preferably 1:1~5:1.By by (C) mercaptan compound and (D1) urea
The ratio of compound is set as above range, so as to obtain effect of the invention better.
It as (D2) melamine based compound, is not particularly limited, as commercially available product, SANWA can be enumerated
Nikalac MW-30HM, Nikalac MW-390, Nikalac MW-100LM, the Nikalac of CHEMICAL CO., LTD.
MX-750LM etc..
(D2) melamine based compound can be used singly or in combination of two or more.(D2) melamine
The compounding amount of amine compound is preferably 0.1~30 mass %, more preferably 1~20 in terms of composition solid ingredient total amount benchmark
Quality %.By being set as above range, to improve residual film ratio, the developability of thick light-sensitive surface on metallic substrates, energy are improved
It is enough to obtain more good pattern form after development.
In addition, the ratio as (C) mercaptan compound and (D2) melamine based compound, preferably (C) mercaptan compound
It is fewer than (D2) melamine based compound.Especially in terms of quality criteria, compounding amount/(D2) melamine of (C) mercaptan compound
The ratio of the compounding amount of amine compound be preferably 0.01:1~less than 1:1, more preferably 0.1:1~0.8:1.By by (C)
The ratio of mercaptan compound and (D2) melamine based compound is set as above range, so as to obtain the present invention better
Effect.
Miscible agent can be matched in photosensitive polymer combination of the invention.As solvent, as long as making (A) polybenzoxazoles
In precursor, (B) emulsion, (C) mercaptan compound, (D) urea compounds and melamine based compound at least any one and
Other any additive dissolutions, are just not particularly limited.As the concrete example of solvent, N can be enumerated, N '-dimethyl formamide,
N-Methyl pyrrolidone, N- ethyl-2-pyrrolidone, N, N '-dimethyl acetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-
Butyrolactone, α-acetyl group-gamma-butyrolacton, tetramethylurea, 1,3- dimethyl-2-imidazolinone, n-cyclohexyl-2-pyrrolidone,
Dimethyl sulfoxide, hexamethyl phosphoramide, pyridine, diethylene glycol monomethyl ether.They can be used alone, and can also be used in mixed way two
Kind or more.The amount of the solvent used can according to coating film thickness, viscosity, relative to 100 mass parts of (A) polybenzoxazoles precursor with
The range of 50~9000 mass parts uses.
In addition, by adding crosslinking agent, silane coupling agent, can be improved film in photosensitive polymer combination of the invention
Physical property, adaptation, be preferred.As crosslinking agent and silane coupling agent, it can be suitable for selecting using well known substance, not have
Especially limitation.
In turn, it can also be compounded within the scope of the effect of the invention in photosensitive polymer combination of the invention
For improving the well known sensitizer of sensitivity, for improving with the well known bonding additives of the cementability of substrate etc..
In turn, in addition, may be used also in photosensitive polymer combination of the invention to assign processing characteristics, various functionality
To be compounded the low molecule or high-molecular compound of other various organic or inorganics.Can be used for example surfactant, levelling agent,
Plasticizer, particle etc..Include organic fine particles, colloidal silicon dioxide, carbon, the stratiform silicon such as polystyrene, polytetrafluoroethylene (PTFE) in particle
The inorganic particles such as hydrochlorate.In turn, various colorants and fiber etc. can also be compounded in photosensitive polymer combination of the invention.
Photosensitive polymer combination of the invention can be eurymeric, or minus in the case where eurymeric, can obtain
More significant effect is preferred.
[dry film]
Resin layer obtained from being dried after the photosensitive polymer combination that dry film of the invention has coating of the invention.
Dry film of the invention is laminated to use in a manner of contacting resin layer with substrate.
Dry film of the invention can be such as manufacture of getting off: utilizing knife type coater, lip coating machine, comma coating machine, film
The suitable method such as coating machine is equably coated with photosensitive polymer combination of the invention and progress on carrier film (support membrane)
Dry, to form aforementioned resin layer, thus preferred laminated cover film (protective film) on it manufactures dry film.Cover film and load
Body film can be same thin membrane material, and different films also can be used.
In dry film of the invention, the thin-film material of carrier film and cover film be can be used as film used in dry film
It is any number of well known to material.
As carrier film, the polyester film such as the polyethylene terephthalate of 2~150 μm of thickness can be used
Equal thermoplastic films.
As cover film, polyethylene film, polypropylene film etc. can be used, preferably compare carrier with the bonding force of resin layer
Film is small.
Preferably 100 μm or less of the film thickness of resin layer on dry film of the invention, more preferable 5~50 μm of range.
Using photosensitive polymer combination of the invention, and the pattern film as its solidfied material is, for example, positive light sensitivity tree
In the case where oil/fat composition, manufacture as described below.
Firstly, as step 1, by the way that photosensitive polymer combination is coated on substrate and is dried or from dry
Resin layer is transferred on (lamination) to substrate on film and obtains film.It is on base material as photosensitive polymer combination to be coated with
Method can be used method used in the coating of photosensitive polymer combination all the time, such as is coated with spinner, stick
Method that machine, knife type coater, curtain coater, screen process press etc. are coated carries out spraying coating with Bracewell coater
Method and ink-jet method etc..As the drying means of film, can be used using air-dry, the heat drying of baking oven or hot plate,
The methods of vacuum drying.In addition, the drying of film is not causing (A) polybenzoxazoles precursor in photosensitive polymer combination
It carries out being ideal under the conditions of closed loop is such.Specifically, can be spontaneously dried, blow and dry or with 70~140
DEG C, 1~30 minute condition is thermally dried.It is preferred that carrying out drying in 1~20 minute on hot plate.Alternatively, it is also possible to vacuum
It is dry, in this case, can at room temperature, 20 minutes~1 hour condition carries out.
It about substrate, is not particularly limited, can be widely applied to semiconductor substrates such as Silicon Wafer, circuit board, various
The substrate of the formation such as resin, metal.
Then, as step 2, by having figuratum photomask or be directly exposed to above-mentioned film.Exposure light
Use the light that the photoacid generator as (B) emulsion can be made to activate and generate sour wavelength.Specifically, exposure light is excellent
Maximum wavelength is selected to be in the range of 350~410nm.As described above, if being suitable for that can adjust sensitivity using sensitizer.Make
For exposure device, contact photoetching machine (contact aligner), mirror surface projection, stepper, laser direct imaging can be used
Exposure device etc..
Then, it as step 3, can be heated, close a part of (A) the polybenzoxazoles precursor in unexposed portion
Ring.Herein, closed loop rate is 30% or so.Heating time and heating temperature are according to (A) polybenzoxazoles precursor, coating film thickness and work
For the photoacid generator of (B) emulsion type and carry out be suitable for change.
Then, as step 4, film is handled with developer solution.The exposed portion in film is removed as a result, from
And it is capable of forming the pattern film of photosensitive polymer combination of the invention.
As method used in development, the developing method of previously known photoresist can choose, such as rotate
Spray-on process stirs method, with any means 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, it can be to addition in them
The water-miscible organic solvents such as methanol, ethyl alcohol, the isopropanol of appropriate amount, surfactant.Thereafter, as needed with flushing liquor to painting
Film is cleaned, and pattern film is obtained.It, can be by the exclusive uses such as distilled water, methanol, ethyl alcohol, isopropanol or group as flushing liquor
It closes and uses.In addition, above-mentioned solvent can be used as developer solution.
Thereafter, as step 5, pattern film is heated, obtains cured coating film (solidfied material).At this point, making (A) polyphenyl simultaneously
Oxazole precursor closed loop, obtains polybenzoxazoles.Heating temperature can be can make the cured side of pattern film of polybenzoxazoles
Formula is being suitable for setting.For example, carrying out heating in 5~120 minutes or so in non-active gas, at 150~350 DEG C.Heating
The preferred range of temperature is 200~300 DEG C.Heating is by using such as hot plate, baking oven, the heating for capableing of set temperature program
Formula baking oven carries out.Air can be used as atmosphere (gas) at this time, the non-active gas such as nitrogen, argon gas can be used.
It should be noted that in the case that photosensitive polymer combination of the invention is negative light-sensitive resin combination,
As (B) emulsion, photoacid generator is replaced using Photoepolymerizationinitiater initiater or Photobase generator, uses developer solution in above-mentioned steps 4
Film is handled, is thus removed the unexposed portion in film, so as to form photoresist group of the invention
Close the pattern film of object.
The purposes of photosensitive polymer combination of the invention is not particularly limited, for example, being suitable for use as printer's ink or bonding
The forming material of agent or display device, semiconductor device, electronic component, optical component or construction material.Specifically, for
The forming material of display device can be used for colour filter, flexible display with thin as layer forming material, Image forming material
Film, anticorrosive additive material, alignment films etc..In addition, the forming material as semiconductor device, can be used for anticorrosive additive material, buffering
Layer forming material etc. as film.It in turn, can as sealing material, layer forming material for the forming material of electronic component
For printed circuit board, interlayer dielectric, wiring cover film etc..In turn, for the forming material of optical component, as optics
Material, layer forming material can be used for hologram, optical waveguide, optical circuit, photoelectricity circuit unit, antireflection film etc..In turn, as
Construction material can be used for coating, smears etc..
Photosensitive polymer combination of the invention is used mainly as pattern forming material, for the pattern being consequently formed
Film plays the function of assigning the ingredient of heat resistance, insulating properties as the permanent film formed by polybenzoxazoles, therefore can be with
Be especially suitable for semiconductor device, the surface protection film of display body device and light emitting device, interlayer dielectric, it is routed uses absolutely again
Velum, flip-chip device protective film, the protective film of device with projection cube structure, the interlayer dielectric of multilayer circuit, nothing
Protective film and liquid crystal orientation film of the printed circuit boards such as source block insulating materials, solder mask, cover film etc..
[embodiment]
Hereinafter, with embodiment, the present invention will be described in more detail, but the present invention is not limited to the following examples.It needs
Illustrate, hereinafter, when in the presence of " part " and " % ", unless otherwise specified, then all quality criterias.
(synthesis of polybenzoxazoles (PBO) precursor (PHA))
N-Methyl pyrrolidone 212g is put into 0.5 liter that has blender, thermometer of flask, stirring and dissolving is double
(3- amino-4-hydroxy amide phenyl) hexafluoropropane 28.00g (76.5mmol).Thereafter, flask is impregnated in ice bath, side will be burnt
0~5 DEG C is remained in bottle, while 4- diphenyl ether dicarboxyl acyl chlorides 25.00g (83.2mmol) is in a solid state with 30 minutes by 4
It is added, each 5g, carries out stirring for 30 minutes in ice bath.Thereafter, continue stirring 5 hours at room temperature.By agitated solution
Investment recycles precipitate into the ion exchange water (resistivity value 18.2M Ω cm) of 1L.Thereafter, it is dissolved in obtained solid
Acetone 420mL, puts into the ion exchange water of 1L.After recycling the solid being precipitated, it is dried under reduced pressure, to obtain carboxyl terminal
Polybenzoxazoles (PBO) precursor (PHA) with following repetitive structures.The number-average molecular weight of polybenzoxazoles precursor (PHA)
It (Mn) is 12900, weight average molecular weight (Mw) is 29300, Mw/Mn 2.28.
(embodiment 1~11, comparative example 1~4)
Relative to above-mentioned 100 mass parts of polybenzoxazoles precursor (PHA), it is compounded the diazo naphthoquinone compound as emulsion
(DNQ) after the additive recorded in (Triratna Chemical Co., Ltd. TKF-428) 10 mass parts and following table 1, table 2, so that poly-
Benzoxazoles precursor is added N-Methyl pyrrolidone (NMP) and varnish is made as the mode of 30 mass %, and preparation embodiment 1~
11, the photosensitive polymer combination of comparative example 1~4.
For the photosensitive polymer combination of the embodiment 1~11, comparative example 1~4 that are prepared, evaluation pattern generating shape,
Resolution ratio.Evaluation method is as follows.
(production method that dry coating is used in evaluation)
Above-mentioned photosensitive polymer combination is coated on copper covering wafer with spinner, it is 4 points dry at 120 DEG C with hot plate
Clock, the dry coating for the photosensitive polymer combination that the film thickness after being dried is 10 μm.
(evaluation of pattern form)
For obtained dry coating, 600mJ/cm is irradiated by figuratum mask is carved using high-pressure sodium lamp2Width
Wavelength light.It after exposure, carries out developing for 30 seconds in 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, be rushed with water
It washes, obtains eurymeric pattern.
For obtained eurymeric pattern, using contact pin type surface-profile measuring instrument Dektak, in adamantine contact pilotage
Under, make sample stage linear movement on accurate reference surface, thus measure the surface shape and ripple of the eurymeric pattern.It is based on
Evaluation criteria shown in FIG. 1 evaluates the cross sectional shape based on eurymeric pattern obtained from the measurement result.The upper section of Fig. 1
Indicate the cross section profile data obtained using Dektak, lower section indicates the schematic section of the cross sectional shape of pattern.A: by pattern
Cross sectional shape top become it is thin and circle situation be denoted as ×, B: by development when exposure portion film removal it is insufficient,
The case where remaining a large amount of drosses on metal substrate be also denoted as ×, C: be regular quadrangle/taper by the cross sectional shape of pattern
The case where shape, is denoted as 〇.
(evaluation of resolution ratio)
Using electron microscope (SEM), directly observation is obtained dry by the production method of above-mentioned evaluation dry coating
The pattern form of dry film (10 μm of film thickness), measurement can be with the cross sectional shapes of pattern for four regular sides under high light exposure
The size (μm) at line-interval (line and space) that shape/conical by its shape is developed.
Their result is shown in together in following tables.In addition, showing embodiment 4 and Comparative Examples 1 and 2 in Fig. 2~4
The cross section profile data obtained using Dektak.
[table 1]
[table 2]
* 1) diazo naphthoquinone compound (Triratna Chemical Co., Ltd. TKF-428)
* 2) TML (following structural formula compound represented)
* 3) D, L- dithiothreitol (DTT) (following structural formula compound represented)
* 4) 2 mercapto ethanol (following structural formula compound represented)
* 5) 1,3- diphenyl urea (following structural formula compound represented)
* 6) melamine based compound (SANWA CHEMICAL CO., LTD. system)
As in above-mentioned table and as shown in the figure, for comprising mercaptan compound but without urea compounds or melamine series
The comparative example 1,3 for closing object, can be obtained high resolution ratio, but residual film ratio is poor, pattern form is rounded.In addition, for including urea
It closes object or melamine based compound but is free of the comparative example 2,4 of mercaptan compound, developability and residual film ratio are poor, and pattern form becomes
Circle, dross largely remain.In contrast, the equal residual film ratio of each embodiment is high, and pattern form is also section quadrilateral shape, even if in film
High resolution ratio also can be obtained in thick 10 μm of thick light-sensitive surface.In addition, according to embodiment 2 and embodiment 6, embodiment 8 and implementing
The comparison of example 11 is it is found that by addition crosslinking agent, resolution ratio is improved.
Claims (5)
1. a kind of photosensitive polymer combination, which is characterized in that contain:
(A) polybenzoxazoles precursor,
(B) emulsion,
(C) mercaptan compound and
(D) at least any one in urea compounds and melamine based compound.
2. a kind of dry film, which is characterized in that go forward side by side with photosensitive polymer combination described in claim 1 is coated on film
Resin layer obtained from row is dry.
3. a kind of solidfied material, which is characterized in that as described in photosensitive polymer combination described in claim 1 or claim 2
The resin layer of dry film formed.
4. a kind of printed circuit board, which is characterized in that have solidfied material as claimed in claim 3.
5. a kind of semiconductor element, which is characterized in that have solidfied material as claimed in claim 3.
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| JP2017-148611 | 2017-07-31 | ||
| JP2017148611A JP2019028316A (en) | 2017-07-31 | 2017-07-31 | Photosensitive resin composition, dry film, cured product, printed wiring board, and semiconductor element |
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| JP3509612B2 (en) | 1998-05-29 | 2004-03-22 | 日立化成デュポンマイクロシステムズ株式会社 | Photosensitive polymer composition, method for producing relief pattern, and electronic component |
| US7282323B2 (en) * | 2002-07-11 | 2007-10-16 | Asahi Kasei Emd Corporation | Highly heat-resistant, negative-type photosensitive resin composition |
| JP2004138758A (en) * | 2002-10-17 | 2004-05-13 | Mitsubishi Chemicals Corp | Photosensitive resin composition and image forming material |
| WO2006132962A2 (en) | 2005-06-03 | 2006-12-14 | Fujifilm Electronic Materials U.S.A. Inc. | Novel photosensitive resin compositions |
| JP5446203B2 (en) * | 2008-10-15 | 2014-03-19 | 日立化成デュポンマイクロシステムズ株式会社 | Photosensitive resin composition, method for producing patterned cured film using the resin composition, and electronic component |
| JP5549841B2 (en) * | 2009-09-07 | 2014-07-16 | 日立化成株式会社 | Photosensitive resin composition, photosensitive film for permanent resist, method for forming resist pattern, printed wiring board and method for producing the same, surface protective film and interlayer insulating film |
| US9274422B2 (en) * | 2011-06-15 | 2016-03-01 | Hitachi Chemical Dupont Microsystems, Ltd. | Photosensitive resin composition, method for forming pattern-cured film using photosensitive resin composition, and electronic component |
| JP6364788B2 (en) * | 2014-01-29 | 2018-08-01 | 日立化成デュポンマイクロシステムズ株式会社 | Photosensitive resin composition and method for producing patterned cured film using the same |
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