CN104471482B - The manufacturing method of photoresist element - Google Patents
The manufacturing method of photoresist element Download PDFInfo
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- CN104471482B CN104471482B CN201380038469.8A CN201380038469A CN104471482B CN 104471482 B CN104471482 B CN 104471482B CN 201380038469 A CN201380038469 A CN 201380038469A CN 104471482 B CN104471482 B CN 104471482B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Abstract
The manufacturing method of the good photoresist element of excellent and appearance the subject of the invention is to provide productivity, the manufacturing method of photoresist element is provided, it includes process below: by (a) carboxyl-content with acid equivalent basis for 100~600, and the binder resin that weight average molecular weight is 5000~500000, (b) it is capable of the unsaturated compound of photopolymerization, (c) Photoepolymerizationinitiater initiater, (d) acetone and (e) non-acetone solvent are concocted, process to obtain blending liquid, herein, the quality of (d) acetone is 30 mass of mass %~98 % relative to the ratio of (d) acetone and the total quality for being somebody's turn to do (e) non-acetone solvent, and the ratio of the total solid content in the blending liquid is 30 mass of mass %~80 %；And the blending liquid is applied on supporting layer and is dried, to form the process of photoresist element on the supporting layer.
Description
Technical field
The present invention relates to manufacturing methods of photoresist element etc..
Background technique
Manufacturing method for making the photosensitive polymer combination of printed circuit is generally comprised binder resin, energy
Unsaturated compound, Photoepolymerizationinitiater initiater, dyestuff of enough photopolymerization etc. using methyl ethyl ketone as represent ketone, with ethyl acetate as
The esters of representative, the process dissolved using tetrahydrofuran as ethers of representative etc. for uniform stirring in the solvent of principal component.For example, specially
It describes in sharp document 1 by using methyl ethyl ketone/methoxy-2-propanol=2/1 1- (weight ratio) mixed solvent and to modulate
Photoresist blending liquid.Furthermore it is also possible to use die coating machine etc. that gained blending liquid is uniformly coated to as supporting layer
On polyester film etc., solvent seasoning is made in drying process, obtains photo-sensitive resin stack.Further more, conduct can also be laminated
Polyethylene film of protective layer etc. and the photoresist laminated body for obtaining three-decker.These laminated bodies are commonly referred to as dry film light
It causes resist (hereinafter referred to as " DF ").
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 11-143069 bulletin
Summary of the invention
Problems to be solved by the invention
However, in using existing manufacturing method of the methyl ethyl ketone as the principal component of solvent, binder resin with can
The dissolubility of the additives such as the dissolubility of the unsaturated compound of photopolymerization and dyestuff is insufficient, the filter when filtering blending liquid
Often it is blocked.In addition, being observed in the visual inspection of appearance from the minute asperities on the surface for reducing manufactured DF, reduction
From the perspective of uneven frequency, still there is room for improvement.
Therefore, the manufacturer of the good photoresist element of and appearance excellent the subject of the invention is to provide productivity
Method.
The solution to the problem
The inventors of the present invention have carried out in-depth study repeatedly in order to solve the above problems, as a result, it has been found that, making above-mentioned tune
When closing liquid using the mixed solvent comprising acetone and when making photosensitive polymer combination, productivity is improved, manufactured DF's
Appearance do not have it is unequal, be it is good, have thus completed the present invention.That is, the present invention is as described below.
[1] a kind of manufacturing method of photoresist element comprising process below:
It is 100~600 with acid equivalent basis by (a) carboxyl-content and binder that weight average molecular weight is 5000~500000
With resin,
(b) be capable of photopolymerization unsaturated compound,
(c) Photoepolymerizationinitiater initiater,
(d) acetone and
(e) non-acetone solvent
It is concocted, so that the process for obtaining blending liquid is somebody's turn to do the quality of (d) acetone relative to (d) acetone and is somebody's turn to do herein
(e) ratio of the total quality of non-acetone solvent is the 30 mass % of mass %~98, and the total solid content in the blending liquid
Ratio be 30 mass of mass %~80 %；And
The blending liquid is applied on supporting layer and is dried, to form photoresist element on the supporting layer
Process.
[2] according to the method for [1] Xiang Suoshu, wherein (e) non-acetone solvent is selected from and is made of alcohol, ester and ether
Group.
[3] according to the method for [2] Xiang Suoshu, wherein the alcohol be selected from by methanol, ethyl alcohol, normal propyl alcohol, isopropanol and
The group of n-butanol composition.
[4] according to the method for [3] Xiang Suoshu, wherein the alcohol is ethyl alcohol.
[5] according to the method for [2] Xiang Suoshu, wherein the ester is ethyl acetate.
[6] according to the method for [2] Xiang Suoshu, wherein the ether is tetrahydrofuran.
[7] method according to any one of [1]~[6] item, wherein the film thickness after the drying of the blending liquid
It is 5 μm~50 μm.
In addition, the present invention also provides manufacture DF's and above-mentioned blending liquid is coated on supporting layer and is dried
It method and protective layer is laminated on the surface for the photo-sensitive resin for being laminated in supporting layer and manufactures the side of the DF of three-decker
Method.
The effect of invention
According to the present invention, provide that productivity is excellent and the manufacturing method of the good photoresist element of appearance.
Detailed description of the invention
Fig. 1 (1) shows the photo of the appearance for the scroll-like laminated body that ocular estimate is S, and it is A that Fig. 1 (2), which shows ocular estimate,
Scroll-like laminated body appearance photo, Fig. 1 (3) show ocular estimate be B scroll-like laminated body appearance photo.
Specific embodiment
Preferred forms (hereinafter referred to as " embodiment ") for carrying out the present invention described further below.Wherein,
The present invention is not limited to embodiments, can carry out within its scope various modifications to implement.
In embodiments, photoresist element can be manufactured by including the method for following process:
It is 100~600 with acid equivalent basis by (a) carboxyl-content and binder that weight average molecular weight is 5000~500000
With resin,
(b) be capable of photopolymerization unsaturated compound,
(c) Photoepolymerizationinitiater initiater,
(d) acetone,
(e) non-acetone solvent and
Other additives of (f) being added as needed
It is concocted, thus the process for obtaining blending liquid；And
The blending liquid is applied on supporting layer and is dried, to form photoresist element on the supporting layer
Process.
Photosensitive element refers to the object for changing property and receiving light.Photosensitive element for example can be film, plate,
The various forms such as thin slice, coiled material, molded product, such as can be comprising photoresist or the object formed by photoresist
Body.More specifically, by will include that the composition (hereinafter referred to as " photosensitive polymer combination ") of photoresist is coated on
On the supporting layers such as film, the layer (hereinafter referred to as " photo-sensitive resin ") formed by photoresist is laminated on supporting layer and obtains
The photoresist laminated body obtained is preferred as photosensitive element.It should be noted that photosensitive polymer combination can be with
It is arbitrary state (such as liquid, solid, lotion, suspension etc.), but it is preferred that the liquid comprising photoresist is (following
Also referred to as " blending liquid ").In addition, being further laminated by the part of the photo-sensitive resin exposing in photoresist laminated body
Protection materials (such as protective film, combined paper film etc.) are simultaneously batched and the photoresist coiled material that obtains is as photonasty member
Part be it is more preferred, the form by the dry film coiled material of photoresist coiled material entirety or photo-sensitive resin after partially dried is
It is particularly preferred.
Using the thickness of the photoresist element manufactured comprising ingredient (a)~(f) blending liquid (after solvent seasoning
Film thickness) it is preferably 5 μm~50 μm.From the viewpoint of by blending liquid the precision being coated on supporting layer, photoresist element
Thickness preferably adjust to 5 μm or more, on the other hand, from the viewpoint of the drying property in drying process, preferably adjust to 50 μ
M or less.The thickness of photoresist element is more preferably 30 μm~50 μm.
It should be noted that photo-sensitive resin is thinner, resolution ratio is higher, in addition, photo-sensitive resin is thicker, film-strength
It is higher, therefore film thickness can be selected suitably depending on the application.
<blending liquid>
Blending liquid preferably comprises (a) binder resin, (b) is capable of the unsaturated compound of photopolymerization, (c) photopolymerization is drawn
Hair agent, (d) acetone and (e) non-acetone solvent and (f) other additives being added as needed.
In the manufacturing method of photoresist element, the ratio of the total solid content in blending liquid is preferably 30 mass %
~80 mass %.The ratio of total solid content in blending liquid refers to for example by by ingredient (a)~(c) and (f) being dissolved in
(d) solid component concentration of acetone and the blending liquid obtained in (e) non-acetone solvent, in order to obtain the effect for improving coating speed
Fruit, from the viewpoint of the quantity of solvent that control is dry and evaporates, preferably 30 mass % or more, on the other hand, from blending liquid
From the perspective of uniformity, preferably 80 mass % or less.The ratio of total solid content in blending liquid is more preferably 40 matter
Measure the mass of %~60 %.
Hereinafter, being described in detail for ingredient (a)~(f).
(a) binder resin
(a) carboxyl-content of binder resin with acid equivalent basis be 100~600, and weight average molecular weight be 5000~
500000, and used as binder.
(a) carboxyl in binder resin due to assign photoresist element relative to aqueous alkali developability or
Fissility, thus preferably.From the viewpoint of resistance to developability, resolution ratio and adaptation, acid equivalent is preferably 100 or more, another
Aspect, from the viewpoint of developability and fissility, preferably 600 or less.
In addition, from the viewpoint of the thickness of DF is remained uniform, obtained relative to the patience of developer solution, (a) binder
It is preferably 5000 or more with the weight average molecular weight of resin, more preferably 20000 or more.On the other hand, from the sight for maintaining developability
Point sets out, and preferably 500000 hereinafter, more preferably 300000 or less.
Additionally, it is preferred that molecular weight distribution be 1.5 or more, more preferably 2 or more.On the other hand, as the upper limit, preferably
7 hereinafter, more preferably 5 or less.
Typically, binder resin (a) is the thermoplastic co-polymer including at least carboxyl group-containing monomer as copolymer composition
Object.Thermoplastic copolymer preferably makes at least one of at least one of following first monomers and following second comonomers altogether
It is poly- and acquisition.
First monomer is the monomer containing carboxyl in molecule.As the first monomer, for example, can enumerate (methyl) acrylic acid,
Fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride and maleic acid half ester etc..Wherein, preferred (methyl) acrylic acid.At this
In specification, (methyl) acrylic acid indicates acrylic or methacrylic acid.
Second comonomer be nonacid and molecule in at least one polymerism unsaturated group monomer.As second
Monomer can enumerate such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl)
Isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl)
Acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- hydroxypropyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- ethyl hexyl
The esters of the vinyl alcohols such as ester, (methyl) benzyl acrylate, vinylacetate；(methyl) acrylonitrile, styrenic monomers (such as benzene
Ethylene and the styrene derivative that can polymerize) etc..Wherein, preferably (methyl) methyl acrylate, (methyl) n-butyl acrylate,
Styrene and (methyl) benzyl acrylate, and from the viewpoint of resolution ratio, particularly preferably use styrene.
(a) binder resin is preferably by mixing the first monomer and second comonomer and with solvent such as third
It is appropriate to add radical polymerization initiator such as benzoyl peroxide, idol in solution made of ketone, methyl ethyl ketone or isopropanol
Nitrogen isobutyronitrile carries out heating stirring to synthesize.Also sometimes while in reaction solution be added dropwise mixture it is a part of while synthesized.
Also it adds a solvent in (a) binder resin, adjusts to required concentration again after the reaction sometimes.As synthesis
Means can also use bulk polymerization, suspension polymerisation or emulsion polymerization other than polymerisation in solution.
In (a) binder resin, the preferred copolymerization ratios of the first monomer and second comonomer are: the first monomer is 10 matter
The mass % of %~60 is measured, and second comonomer is 40 mass of mass %~90 %.It is even more preferred that the first monomer be 15 mass %~
35 mass %, and second comonomer is 65 mass of mass %~85 %.
As the more specific example of (a) binder resin, such as can enumerate containing methyl methacrylate, methyl
The polymer of acrylic acid and styrene as copolymer composition contains methyl methacrylate, methacrylic acid and the positive fourth of acrylic acid
Polymer of the ester as copolymer composition, and contain benzyl methacrylate, methyl methacrylate and acrylic acid 2- ethyl hexyl
Polymer etc. of the ester as copolymer composition.
In embodiments, (a) binder resin in photoresist element content (be explained, relative to
The solid component total amount of photoresist element.Below respectively contain ingredient in it is identical, unless otherwise prescribed) be 20 mass %~
The range of 90 mass %, preferred lower limit are 25 mass %, and the preferred upper limit is 75 mass %, and preferred lower limit is 40 matter
% is measured, the preferred upper limit is 65 mass %.From the viewpoint of maintaining alkali-developable, the content be preferably 20 mass % with
On, on the other hand, from the viewpoint of giving full play to as the performance of resist the corrosion-resisting pattern formed by exposure preferably
90 mass % or less.
(b) it is capable of the unsaturated compound of photopolymerization
(b) unsaturated compound for capableing of photopolymerization is that for example have addition polymerization and with ethylenic unsaturated bond
Monomer.Ethylenic unsaturated bond is preferably terminal ethylenic unsaturated group.
It is capable of the specific example of the unsaturated compound of photopolymerization as (b), such as preferably distinguishes at the both ends of bisphenol-A
The dimethylacrylate of the polyethylene glycol of the ethylene oxide of the average Unit 1 of addition distinguishes addition at the both ends of bisphenol-A
The dimethylacrylate of the polyethylene glycol of the ethylene oxide of average Unit 2 distinguishes average 5 list of addition at the both ends of bisphenol-A
The dimethylacrylate of the polyethylene glycol of the ethylene oxide of member distinguishes the epoxy of the average Unit 7 of addition at the both ends of bisphenol-A
The dimethylacrylate of the polyethylene glycol of ethane distinguishes the ethylene oxide peace of the average Unit 6 of addition at the both ends of bisphenol-A
The dimethylacrylate of the polyalkylene glycol of the propylene oxide of equal Unit 2 distinguishes addition average 15 at the both ends of bisphenol-A
The dimethylacrylate of the polyalkylene glycol of the propylene oxide of the ethylene oxide of unit and average Unit 2.
It, being capable of photopolymerization as (b) from the viewpoint of high-resolution, the stripping performance of cured film and cured film flexibility
Unsaturated compound, such as preferred seven glycol dipropylene glycol acrylate of 4- nonyl phenyl or eight glycol propylene of 4- nonyl phenyl
Acid esters, 4- nonyl phenyl tetraethylene glycol acrylate, five methacrylatoethyl of 4- octyl phenyl etc..
It is capable of the specific example of the unsaturated compound of photopolymerization as others (b), such as acrylic acid 2- can be enumerated
Hydroxyl -3- phenoxy propyl ester, phthalic anhydride and the half ester compound of acrylic acid 2- hydroxypropyl acrylate are reacted with propylene oxide
Object, 1,6-hexylene glycols two (methyl) acrylate, 1,4- cyclohexanediol two (methyl) acrylate, 2- bis- (p-hydroxybenzene) third
Alkane two (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons penta
Tetrol six (methyl) acrylate, trihydroxymethylpropanyltri diglycidyl ether three (methyl) acrylate, bis- (the 4- methyl-props of 2,2-
Five ethoxyl phenenyl of alkene acyloxy) propane, glycerol tri-acrylate, will trimethylolpropane implement acroleic acid esterification made of three
Acrylate, on pentaerythrite the glycol of average 4 moles of the ethylene oxide of addition tetraacrylate and isocyanuric acid ester
The multifunctional (methyl) acrylate etc. of compound.They can be used alone, and can also be used in combination of two or more.
The content for the unsaturated compound that (b) in photoresist element is capable of photopolymerization is preferably 5 mass %~75
The range of quality %.From the viewpoint of inhibiting solidify the bad delay with developing time, the content be preferably 5 mass % with
On, more preferably 15 mass % or more, further preferably 30 mass % or more.On the other hand, anti-from inhibition cold flow and solidification
From the perspective of losing the removing delay of agent, which is preferably 75 mass % hereinafter, more preferably 60 mass % are hereinafter, further
Preferably 50 mass % or less.
(c) Photoepolymerizationinitiater initiater
(c) Photoepolymerizationinitiater initiater is the compound for making monomer polymerization by light.As (c) Photoepolymerizationinitiater initiater, Ke Yishi
Locality is particularly preferably double using six aryl using the substance for example used usually as the Photoepolymerizationinitiater initiater of photoresist
Imidazoles (hereinafter also referred to triarylimidazoles dimer).
It as triarylimidazoles dimer, such as can enumerate: 2- (o- chlorphenyl) -4,5- diphenyl-imidazole dimer
(hereinafter also referred to " 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-tetraphenyl -1,1 '-bis- imidazoles "), 2,2 ', 5- tri--(o- chlorine
Phenyl) -4 ', 5 '-diphenyl-imidazole dimer of -4- (3,4- Dimethoxyphenyl), 2,4- be bis--(o- chlorphenyl) -5- (3,4-
Dimethoxyphenyl)-diphenyl-imidazole dimer,
2,4,5- tri--(o- chlorphenyl)-diphenyl-imidazole dimer, 2- (o- chlorphenyl)-bis- -4,5- (3,4- diformazan
Phenyl)-imidazoles dimer, 2,2 '-bis--(2- fluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimerization
Body, 2,2 '-bis--(2,3- difluoromethyl phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimers, it is 2,2 '-bis- -
(2,4 difluorobenzene base) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimer,
2,2 '-bis--(2,5- difluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimers, 2,2 ' -
Double-(2,6- difluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimer, 2,2 '-bis--(2,3,4- trifluoros
Phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimers, 2,2 '-bis--(2,3,5- trifluorophenyls) -4,4 ', 5,
5 '-four-(3- methoxyphenyl)-imidazoles dimers,
2,2 '-bis--(2,3,6- trifluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimers, 2,2 ' -
Double-(2,4,5- trifluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimer, 2,2 '-bis--(2,4,6- tri-
Fluorophenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimers,
2,2 '-bis--(2,3,4,5- tetrafluoro phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimers, 2,
2 '-bis--(2,3,4,6- tetrafluoro phenyl) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimers and 2,2 '-bis--(2,
3,4,5,6- pentafluorophenyl group) -4,4 ', 5,5 '-four-(3- methoxyphenyl)-imidazoles dimers etc..
In particular, 2- (o- chlorphenyl) -4,5- diphenyl-imidazole dimer is for resolution ratio or solidification film strength against corrosion
Photoepolymerizationinitiater initiater with very high effect it is preferable to use.The above-mentioned triarylimidazoles dimer enumerated can individually make
With, or can be used in combination of two or more.In addition, the above-mentioned triarylimidazoles dimer enumerated can be with following acridines
Object, pyrazoline compounds etc. are closed to be applied in combination.
As (c) Photoepolymerizationinitiater initiater, acridine compounds or pyrazoline compounds can be properly used.As acridine
Object is closed, such as acridine, 9- phenylacridine, 9- (4- tolyl)-acridine, 9- (4- methoxyphenyl) acridine, 9- (4- can be enumerated
Hydroxyphenyl) acridine, 9- ethyl acridine, 9- chloroethyl acridine, 9- methoxyacridine, 9- ethyoxyl acridine,
9- (4- aminomethyl phenyl) acridine, 9- (4- ethylphenyl) acridine, 9- (4- n-propyl phenyl) acridine, 9- (the positive fourth of 4-
Base phenyl) acridine, 9- (4- tert-butyl-phenyl) acridine, 9- (4- ethoxyl phenenyl) acridine, 9- (4- acetylphenyl) acridine, 9-
(4- dimethylaminophenyl) acridine, 9- (4- chlorphenyl) acridine,
9- (4- bromophenyl) acridine, 9- (3- aminomethyl phenyl) acridine, 9- (3- tert-butyl-phenyl) acridine, 9- (3- acetyl group
Phenyl) acridine, 9- (3- dimethylaminophenyl) acridine, 9- (3- diethylamino phenyl) acridine, 9- (3- chlorphenyl) acridine,
9- (3- bromophenyl) acridine, 9- (2- pyridyl group) acridine, 9- (3- pyridyl group) acridine, 9- (4- pyridyl group) acridine etc..Wherein, 9-
Phenylacridine is preferred.
As pyrazoline compounds, such as 1- phenyl -3- (4- tert-butyl-styrene base) -5- (tertiary fourth of 4- can be enumerated
Base-phenyl)-pyrazoline, 1- (4- (benzoxazoles -2- base) phenyl) -3- (4- tert-butyl-styrene base) -5- (4- tert-butyl -
Phenyl)-pyrazoline, 1- phenyl -3- (4- xenyl) -5- (4- tbutyl-phenyl)-pyrazoline, 1- phenyl -3- (4- biphenyl
Base) -5- (4- t-octyl-phenyl)-pyrazoline etc..
As (c) Photoepolymerizationinitiater initiater in addition to the foregoing, for example, can enumerate 2- ethyl hydrazine, octaethyl anthraquinone,
1,2 benzae thracene quinone, 2,3- benzo anthraquinone, 2- phenyl anthraquinone, 2,3- diphenyl anthraquinone, 1- chloroanthraquinone, 1,4- naphthoquinones, 9,10- are luxuriant and rich with fragrance
The quinones such as quinone, 2-MNQ, 2,3- dimethyl anthraquinone and 3- chloro-2-methyl anthraquinone, benzophenone, Michler's keton [4,
4 '-bis- (dimethylamino) benzophenone] and 4, the aromatic ketones such as 4 '-bis- (diethylamino) benzophenone, benzoin,
The benzoin ethers such as benzoin ethyl ether, benzoin phenylate, methylbenzoin and ethyl benzoin, benzil dimethyl ketal, benzene
Even acyl diethyl ketal, the combination of thioxanthene ketone class and alkyl amino benzoic acid, 1- phenyl -1,2- propanedione -2-O- cupron,
The oximes esters such as 1- phenyl -1,2- propanedione -2- (O- ethoxy carbonyl) oxime.
Wherein, the combination as above-mentioned thioxanthene ketone class and alkyl amino benzoic acid, for example, can enumerate ethyl thioxanthones with
The combination of dimethyl amino benzoate, the combination of 2-chlorothioxanthone and dimethyl amino benzoate and isopropyl thiophene
Ton ketone and the combination of dimethyl amino benzoate etc..In addition, N- aryl ammonia can be used as (c) Photoepolymerizationinitiater initiater
Base acid.As the example of N- aryl amino acid, N-phenylglycine, N- Methyl-N-phenyl glycine, N- ethyl-can be enumerated
N-phenylglycine etc..Wherein, particularly preferred N-phenylglycine.
The content of (c) Photoepolymerizationinitiater initiater in photoresist element is the range of 0.01 mass of mass %~30 %,
Preferred lower limit is 0.05% mass %, and further preferred lower limit is 0.1 mass %, and the preferred upper limit is 15 matter
% is measured, the further preferred upper limit is 10 mass %.Go out from the viewpoint for obtaining sufficient sensitivity when photopolymerization using exposure
Hair, (c) content of Photoepolymerizationinitiater initiater is preferably 0.01 mass % or more, on the other hand, from making light fully saturating when photopolymerization
From the perspective of crossing to the bottom surface of photoresist element (that is, part far from light source), obtaining fine resolution and adaptation,
Preferably 30 mass % or less.
(d) acetone and (e) non-acetone solvent
Blending liquid includes (d) acetone and (e) non-acetone solvent.Blending liquid be by by above-mentioned (a) binder resin, on
State unsaturated compound that (b) is capable of photopolymerization and/or above-mentioned (c) Photoepolymerizationinitiater initiater in any order or disposably
It is dissolved in (d) acetone and/or (e) non-acetone solvent and mix to acquisition.
For example, can by (a) binder resin in the in the mixed solvent dissolution of (d) acetone and (e) non-acetone solvent and
Formed varnish, in the varnish dissolve (b) be capable of the unsaturated compound of photopolymerization, (c) Photoepolymerizationinitiater initiater and/or (f) its
His additive, obtains thick blending liquid, and by the thick blending liquid, with (d) acetone and/or (e) non-acetone solvent is further mixed as needed
It closes, to obtain the blending liquid with required solid component concentration.Therefore, (a) binder resin can be poly- by solution
It closes or suspension polymerisation obtains, (a) binder resin obtained by polymerisation in solution can contain (d) acetone as solvent
Or (e) at least one of non-acetone solvent.(a) solvent contained in binder resin also rises as the solvent of blending liquid
Effect, therefore in the concentration or viscosity for seeking the solid component in blending liquid, it is calculated as solvent.
As long as (e) solvent other than non-acetone solvent acetone, is not particularly limited it.Preferably selected from by
(i) ether of the ester using ethyl alcohol as the alcohol of representative, (ii) using ethyl acetate as representative and (iii) using tetrahydrofuran as representative forms
At least one of group.In addition, (e) non-acetone solvent be more desirably selected from by methanol, ethyl alcohol, normal propyl alcohol, isopropanol and
At least one of the group of n-butanol composition, particularly preferably ethyl alcohol.
In particular, using polar solvent compared with the blending liquid made of (d) acetone being used only or modulate using only methyl ethyl ketone
Be the alcohol of representative as (e) non-acetone solvent using ethyl alcohol, the unsaturated compound and/or dye of photopolymerization are capable of from raising (b)
It is preferred from the perspective of the dissolubilities of (f) other additives such as material.
In addition, use alcohol as (e) non-acetone solvent, from being intended to reduce the viscosity of blending liquid, can higher set
It is preferred from the viewpoint of solid component concentration and then raising productivity in blending liquid.
In addition, from the viewpoint of in drying process will dry film surface while remain good removal solvent, use
Alcohol as (e) non-acetone solvent be preferred, that is, from improve blending liquid coating speed, improve photosensitive element productivity
From the perspective of be preferred.It should be noted that described here refers to film " while dry film surface is remained good "
The flatness on surface is high and the appearance unevenness by being visually observed is lacked.
(d) quality of acetone is preferred relative to the ratio of the total quality of above-mentioned (d) acetone and above-mentioned (e) non-acetone solvent
For 30 mass % or more, more preferably 40 mass % or more, further preferably 50 mass % or more, particularly preferably 60 matter
Measure % or more.On the other hand, as the upper limit, preferably 98 mass % hereinafter, more preferably 90 mass % are hereinafter, further preferably
For 80 mass % hereinafter, particularly preferably 70 mass % or less.
In addition, the ratio as the total solid content in blending liquid, preferably 30 mass % or more, more preferably 40 matter
Measure % or more, further preferably 50 mass % or more.On the other hand, as the upper limit, preferably 80 mass % or more, more preferably
For 70 mass % hereinafter, further preferably 60 mass % or less.
The viewpoint of the flatness of film surface after improving drying reduces the uncoated portion of pinprick etc. in drying process
These ratio sets in such range are suitable by viewpoint and from the perspective of obtaining good coated face.
In the present embodiment, (d) quality of acetone relative to the total of above-mentioned (d) acetone and above-mentioned (e) non-acetone solvent
The ratio of quality and the ratio set of the total solid content in blending liquid are counted in range as described above.
It should be noted that by the way that such invention specific item in conjunction with other invention specific items, is realized production
Rate is excellent and the manufacturing method of the good photoresist element of appearance.It is not yet clear for the details of its mechanism, it is believed that be
By the way that acetone ratios or solid component ratio set in particular range, can be suitably controlled the drying of solvent, suitably be maintained
The flatness of film surface when dry.
In addition, as above-mentioned (e) non-acetone solvent, preferably comprise ethyl alcohol as principal component (preferably 50 mass % or more, more
It is preferred that 70 mass % or more, further preferably 90 mass % or more, or 100 mass %).
In addition, the viscosity as above-mentioned blending liquid, is preferably 500Pasec~4000mPa with the viscosimeter at 25 DEG C
sec。
(f) other additives
In blending liquid other than ingredient (a)~(e), (f) other additives can be contained.Specifically, (f) other add
Add agent including, for example, coloring materials such as dyestuff, pigment.As such coloring material, base dye can be used.Based on
Dyestuff, for example, can enumerate Viride Nitens 1 [CAS serial number (same as below): 633-03-4], malachite green oxalate [2437-29-8],
Brilliant green [633-03-4], magenta [632-99-5], crystal violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet
[548-62-9], methyl green [82-94-0], victoria blue B [2580-56-5], Blue 7 [2390-60-5], rhodamine B
[81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2] etc..Wherein, preferably Viride Nitens 1, peacock green oxalic acid
Salt and Blue 7, from the viewpoint of improving form and aspect stability and exposure contrast, particularly preferred Viride Nitens 1 and Blue 7.
The content of coloring material in photoresist element is preferably 0.001 mass of mass %~1 %.Coloring material
Content be 0.001 mass % or more when, have the effect of improve treatability, be therefore preferred, another aspect, 1 mass % with
When lower, have the effect of maintaining storage stability, be therefore preferred.
In addition, color developing agent such as color appearance system can be contained in blending liquid in order to assign visual image by exposure
Dyestuff etc..As this colour developing based dye, such as the combination of leuco dye or fluoran dyes and halogen compounds can be enumerated
Deng.
As leuco dye, for example, can enumerate three (4- dimethylamino -2- aminomethyl phenyl) methane [leuco crystal violet],
Three (4- dimethylamino -2- aminomethyl phenyl) methane [leucomalachite green] and fluoran dyes etc..When wherein, using leuco crystal violet
Contrast is good, is preferred.
As halogen compounds, such as amyl bromide, isoamyl bromide, brominated isobutylene, ethylene bromide, diphenyl can be enumerated
Methyl bromide, benzal bromide (benzal bromide), methylene bromide, trisbromomethyl phenyl sulfone, carbon tetrabromide, tricresyl phosphate (2,3-
Dibromopropyl) ester, trichloroacetamide, amyl iodide, isobutyl iodide, bis- (rubigan) ethane of the chloro- 2,2- of 1,1,1- tri-, hexachloroethanc
Alkane, chlorination triaizine compounds etc..
The content of color developing agent in photoresist element is preferably each independently 0.1 mass of mass %~10 %.
In addition, preferably containing in blending liquid to improve the thermal stability of photosensitive polymer combination and storage stability
By at least one or more in the group being made of radical polymerization inhibitor or benzotriazole and carboxyl benzotriazole class
Close object.
As radical polymerization inhibitor, such as p methoxy phenol, quinhydrones, pyrogallol, naphthylamines, tert-butyl o can be enumerated
Benzenediol, stannous chloride, 2,6- di-t-butyl-paracresol, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol), 2,2 '-
Methylene-bis(4-ethyl-6-t-butyl phenol), nitroso phenyl hydroxylamine aluminium salt, diphenyl nitrosamine etc..
As benzotriazole, such as 1,2,3- benzotriazole, 1- chloro- 1,2,3- benzotriazole, bis- (N-2- can be enumerated
Ethylhexyl) aminomethylene-l, 2,3 triazole, bis- (N-2- ethylhexyl) aminomethylene -1,2,3- tolyls three
Azoles, bis- (N-2- ethoxy) aminomethylene-l, 2,3 triazoles etc..
As carboxyl benzotriazole class, such as 4- carboxyl -1,2 can be enumerated, 3- benzotriazole, 5- carboxyl -1,2,3- benzene
And triazole, (N, N- dibutylamino) carboxyl benzotriazole, N- (bis- -2- ethylhexyl of N, N-) aminomethylene carboxyl benzo three
Azoles, N- (bis- -2- ethoxy of N, N-) aminomethylene carboxyl benzotriazole, N- (bis- -2- ethylhexyl of N, N-) aminoethylene
Carboxyl benzotriazole etc..
The total of radical polymerization inhibitor, benzotriazole and/or carboxyl benzotriazole class in photoresist element contains
Amount is preferably 0.001 mass of mass %~3 %, and preferred lower limit is 0.05 mass %, and the preferred upper limit is 1 mass %.
From the viewpoint of assigning storage stability to photosensitive polymer combination, which is preferably 0.001 mass % or more,
From the viewpoint of maintaining sensitivity, preferably 3 mass % or less.
In blending liquid, other plasticizer can be contained as needed.As such plasticizer, such as can enumerate poly-
Ethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxy
The diol-lipids such as propylene monomethyl ether, polyoxyethylene list ether, polyoxypropylene list ether, polyoxyethylene polyoxypropylene list ether；It is poly-
The dehydrated sorbitol derivatives such as ethylene oxide sorbitan laurate esters, polyoxyethylene sorbitan oleate；It is adjacent
The phthalates such as diethyl phthalate；Orthotoluene sulfonamide, para toluene sulfonamide, tributyl citrate, citric acid
Triethyl, CitroflexA-2, three n-propyl of acetyl citrate and acetyl tributyl citrate；In bisphenol-A
The two sides difference addition propylene glycol of propylene oxide, in the two sides of bisphenol-A difference addition ethylene glycol of ethylene oxide etc..
The content of plasticizer in photoresist element is preferably 0.1 mass of mass %~50 %, preferred lower limit
For 1 mass %, the preferred upper limit is 30 mass %.From the sight for inhibiting the delay of developing time, assigning flexibility to cured film
Point sets out, which is preferably 0.1 mass % or more, on the other hand, from the viewpoint of inhibiting solidification insufficient and cold flow, preferably
For 50 mass % or less.
In blending liquid, other antioxidants can be contained as needed.As antioxidant, such as phosphorous can be enumerated
Triphenyl phosphate ester, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, (Dan Renji phenyl) ester of phosphorous acid three and bis- (Dan Renji phenyl)-
Dinonylphenyl phosphite ester etc..
The content of antioxidant in photoresist element is preferably the range of 0.01 mass of mass %~0.8 %, more
Preferred lower limit is 0.01 mass %, and the preferred upper limit is 0.3 mass %.When the content is 0.01 mass % or more, well
Ground shows the effect of the form and aspect excellent in stability of photosensitive polymer combination, and sensitivity when photosensitive polymer combination exposes becomes
It obtains well, is therefore preferred, on the other hand, when which is 0.8 mass % or less, colour rendering is suppressed, therefore form and aspect are steady
It is qualitative to become good, and adaptation also becomes well, to be therefore preferred.
<supporting layer>
Above-mentioned supporting layer is the layer for being used to support the photo-sensitive resin being formed on.In addition, photoresist element
Manufacturing method as needed may include the process for forming protective layer with supporting layer opposite side in photoresist element.
Transparent membrane as supporting layer, preferably through the light emitted from exposure light source.As such film, example
It is thin that pet film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer can such as be enumerated
Film, polyvinylidene chloride film, vinylidene chloride copolymerization film, polymethyl methacrylate copolymer film, polystyrene are thin
Film, polyacrylonitrile film, styrol copolymer film, polyamide film and cellulose derivative film etc..As these films,
Oriented film can be used as needed.The mist degree of supporting layer is preferably 5 or less.About the thickness of supporting layer, relatively thin layer exists
It is advantageous in terms of image formative and economy, but from needing to maintain intensity the thickness, it is preferable to use 10 μm~30 μm
Degree.
<protective layer>
Protective layer preferably have for the closing force with photo-sensitive resin protective layer it is more sufficiently small than supporting layer, can
The property being easily peeled off.For example, polyethylene film and polypropylene film etc. can be used preferably as protective layer.As protection
Layer, can be used for example the excellent film of fissility shown in Japanese Unexamined Patent Application 59-202457 bulletin.The thickness of protective layer
Preferably 10 μm~100 μm, more preferably 10 μm~50 μm.
<manufacturing method of photoresist element>
In the manufacturing method of photoresist element, blending liquid is applied on supporting layer and is dried, thus
The process that photoresist element is formed on supporting layer, can be carried out by coating means and drying means as needed.
As coating means, such as can use spinner, die coating machine, flush coater, dipping, printing, knife type coater, roller coating etc..Make
For drying means, such as it can use air-dried, heated-air drying, light irradiation, hot plate, inertia furnace, the liter for capableing of set temperature program
Warm formula baking oven etc..In addition, the reconciliation of the Multiple components contained in blending liquid and the application of blending liquid and drying can in air or
It is carried out in the atmosphere of the inert gases such as person's nitrogen, argon gas.
Manufactured photoresist element is preferably pacified in the manufacture of printed circuit board, IC chip by the above-mentioned manufacture method
Metal foils Precision Machining, ball grid array (BGA) or the chip size packages (CSP) such as dress is manufactured with lead frame, metal mask manufactures
The manufacture of equal packaging bodies, flip chip (COF) or coil type engage the manufacture of the belts substrate such as (TAB), semiconductor convex block automatically
Manufacture, be subject to benefit in the manufacture of the partition of flat-panel monitors such as tin indium oxide (ITO) electrode or addressing electrode, electromagnetic wave shielding
With.
Manufacturing method according to the present embodiment can improve the photoresist member for being used to form printed circuit well
The appearance of the productivity of part, the DF formed by photoresist element.
Embodiment
Embodiment and comparative example is given below to further illustrate present embodiment, but the present invention is wanted without departing from it
Purport just should not be limited by the examples.
[embodiment 1~12 and comparative example 1~8]
The ingredient for the photosensitive polymer combination recorded in blending table 1 or 2 is stirred dissolution in dissolving tank, passes through
Filter filters blending liquid.Then, use pump conveying blending liquid to die coating machine in the poly terephthalic acid second two as supporting layer
It is equably coated on alcohol ester, and be transported to dry section to make solvent seasoning.Hereafter, it is used as the polyethylene film lamination of protective layer,
Obtain the DF with the thickness for the photosensitive layer recorded in table 1 or 2.In above-mentioned operation, the method shown in following is dissolved
Property evaluation, coating speed evaluation, coating evaluation and ocular estimate.In addition, the weight of the measurement resin of the method shown in following is equal
Molecular weight.As a result shown in table 1 or 2 in.
It should be noted that the GR-16 that the polyethylene terephthalate as supporting layer uses Supreme Being people (strain) to manufacture
(16 μm of thickness), GF-18 (19 μ of thickness manufactured additionally as the polyethylene film of protective layer using Tamapoly Co., Ltd.
m)。
(1) dissolubility is evaluated
According to the stopping state of following grade ratings filters when blending liquid being filtered via filter.Blocking indicates when few
Favorable solubility.
It should be noted that the sieve pore of filter is 3 μm.
A: it is good, absolutely not block.
B: slight blocking occurs, but can filter.
C: plugged filter occurs, cannot be filtered within 1 hour.
(2) coating speed is evaluated
Methyl ethyl ketone is used only as on the basis of the blending liquid recorded in the comparative example 1 of solvent, no uncoated portion is observed
Divide the maximum coating speed for carrying out being coated with uniformly and smoothly.
Then, for each blending liquid, the maximum coating speed that no uncoated portion is carried out uniformly and is smoothly coated with is observed
Degree, is set as 1 for maximum coating speed observed by the blending liquid of comparative example 1, is evaluated with the ratio relative to it.Evaluation
When greater than 1, the maximum coating speed of the blending liquid situation faster than blending liquid of the methyl ethyl ketone as solvent when is used only is indicated.
(3) coating is evaluated
According to the maximum coating speed observed in comparative example 1, the coating of various blending liquids is carried out.It is commented according to following grades
Valence is coated with blending liquid on the polyester as supporting layer by using die coating machine and the state of photo-sensitive resin that obtains.
S: not having uncoated portion, and smoothness is high.
A: there is no uncoated portion, smoothly carried out coating.
B: there is a part of uncoated portion.
C: substantially uncoated portion.
(4) ocular estimate
Use die coating machine to be coated with blending liquid on the polyester as supporting layer and make solvent seasoning, then, is used as protecting
The polyethylene film stacking of layer, for the scroll-like laminated body obtained with supporting layer/photosensitive layer/protective layer three-decker into
Row ocular estimate evaluates (referring to Fig.1) according to following grades.
S: the appearance of the coiled material product of three-decker is that surface is uniform, absolutely not uneven.
A: the appearance of the coiled material product of three-decker is that surface is uniform, there is no unevenness.
B: the appearance of the coiled material product of three-decker be it is uneven, basic whole face has unevenness.
(5) weight average molecular weight
The weight average molecular weight (Mw) of resin is measured by gel permeation chromatography (standard polystyren conversion).For measuring
Pillar be Showa electrician company manufacture trade (brand) name Shodex 805M/806M series connection, standard monodisperse polystyrene selection it is clear
With the Shodex STANDARD SM-105 of electrician (strain) manufacture, developing solvent is n-methyl-2-pyrrolidone, and detector uses
The trade (brand) name Shodex RI-930 of Showa electrician manufacture.
[table 1]
[table 2]
<symbol description>
P-1: 65 mass % of methyl methacrylate, 25 mass % of methacrylic acid, 10 mass % of butyl acrylate three
The methyl ethyl ketone solution (solid component quality ratio 30%, weight average molecular weight 100,000, acid equivalent 344) of membered copolymer
P-2: 65 mass % of methyl methacrylate, 25 mass % of methacrylic acid, 10 mass % of butyl acrylate three
Acetone and alcohol mixed solution (the solvent quality ratio: acetone/ethanol=80/20, solid component quality ratio of membered copolymer
40%, weight average molecular weight 100,000, acid equivalent 344)
P-3: 65 mass % of methyl methacrylate, 25 mass % of methacrylic acid, 10 mass % of butyl acrylate three
Acetone and alcohol mixed solution (the solvent quality ratio: acetone/ethanol=80/20, solid component quality ratio of membered copolymer
75%, weight average molecular weight 100,000, acid equivalent 344)
P-4: 65 mass % of methyl methacrylate, 25 mass % of methacrylic acid, 10 mass % of butyl acrylate three
The acetone soln (solid component quality ratio 32%, weight average molecular weight 100,000, acid equivalent 344) of membered copolymer
P-5: 67 mass % of methyl methacrylate, 23 mass % of methacrylic acid, 10 mass % of butyl acrylate three
The methyl ethyl ketone solution (solid component quality ratio 25%, weight average molecular weight 200,000, acid equivalent 374) of membered copolymer
P-6: 67 mass % of methyl methacrylate, 23 mass % of methacrylic acid, 10 mass % of butyl acrylate three
Acetone and alcohol mixed solution (the solvent quality ratio: acetone/ethanol=80/20, solid component quality ratio of membered copolymer
34%, weight average molecular weight 200,000, acid equivalent 374)
P-7: 50 mass % of methyl methacrylate, 25 mass % of methacrylic acid, the ternary of 25 mass % of styrene are total
The methyl ethyl ketone solution (solid component quality ratio 35%, weight average molecular weight 50,000, acid equivalent 344) of polymers
P-8: 50 mass % of methyl methacrylate, 25 mass % of methacrylic acid, the ternary of 25 mass % of styrene are total
Polymers acetone and alcohol mixed solution (solvent quality ratio: acetone/ethanol=75/25, solid component quality ratio 47%,
Weight average molecular weight 50,000, acid equivalent 344)
P-9: 50 mass % of methyl methacrylate, 25 mass % of methacrylic acid, the ternary of 25 mass % of styrene are total
Methyl ethyl ketone and alcohol mixed solution (the solvent quality ratio: methyl ethyl ketone/ethyl alcohol=75/25, solid component quality ratio of polymers
45%, weight average molecular weight 50,000, acid equivalent 344)
M-1: the dimethyl allene of the polyethylene glycol of average 2 moles of the ethylene oxide of addition is distinguished at the both ends of bisphenol-A
Acid esters (BPE-200 of the village Xin Zhong chemistry (strain) manufacture)
M-2: the dimethyl allene of the polyethylene glycol of average 5 moles of the ethylene oxide of addition is distinguished at the both ends of bisphenol-A
Acid esters (BPE-500 of the village Xin Zhong chemistry (strain) manufacture)
M-3: average 2 moles of the propylene oxide of addition and average 6 moles of ethylene oxide are distinguished at the both ends of bisphenol-A
The dimethylacrylate of polyalkylene glycol
M-4: further in both ends difference addition average 3 on the polypropylene glycol of average 12 moles of the propylene oxide of addition
The dimethylacrylate of the polyalkylene glycol of moles of ethylene oxide
M-5: hexamethylene diisocyanate with low polypropylene glycol monomethacrylate (make by Nippon Yushi (Co., Ltd.)
BLEMMER PP1000) carbamate compound.
M-6: acrylate (the Xin Zhong village chemistry of average 3 moles of the ethylene oxide of addition on trimethylolpropane
The A-TMPT-3EO of (strain) manufacture)
Seven glycol dipropylene glycol acrylate of M-7:4- nonyl phenyl
Bis- (diethylamino) benzophenone of I-1:4,4 '-
I-2:2- (o- chlorphenyl) -4,5- diphenyl-imidazole dimer
D-1: diamond green
D-2: leuco crystal violet
A-1: para toluene sulfonamide
A-2: benzotriazole
A-3: the addition aluminium salt of 3 moles of nitroso phenyl hydroxylamine
A-4: in average 1 mole of the propylene oxide of the both ends of bisphenol-A difference addition, further addition average 1 respectively
Mole glycidyl substance
A-5: in the polypropylene glycol of average 2 moles of the propylene oxide of the both ends of bisphenol-A difference addition
The IRGANOX 245 of A-6: チ バ ス ペ シ ャ リ テ ィ ー ケ ミ カ Le ズ (strain) manufacture
A-7:Newcol 3-85 (Japanese emulsifier (strain) manufacture)
S-1: acetone
S-2: ethyl alcohol
S-3: methyl ethyl ketone
Industrial availability
The photoresist element produced through the invention can manufacture in printed circuit board, IC chip installation lead
The metal foils Precision Machinings such as frame manufacture, metal mask manufacture, the manufacture of the packaging bodies such as BGA or CSP, the belts substrate such as COF or TAB
Manufacture, the manufacture of semiconductor convex block, the manufacture of the partition of the flat-panel monitors such as ITO electrode or addressing electrode, electromagnetic wave shielding
In be used.
Claims (2)
1. a kind of manufacturing method of photoresist element comprising process below:
It is 100~600 with acid equivalent basis by (a) carboxyl-content and binder tree that weight average molecular weight is 5000~500000
Rouge,
(b) be capable of photopolymerization unsaturated compound,
(c) Photoepolymerizationinitiater initiater,
(d) acetone and
(e) ethyl alcohol
It is concocted, so that the process for obtaining blending liquid is somebody's turn to do the quality of (d) acetone relative to (d) acetone and is somebody's turn to do (e) herein
The ratio of the total quality of ethyl alcohol is the 30 mass % of mass %~98, and the ratio of the total solid content in the blending liquid is 30
The mass of quality %~80 %；And
The blending liquid is applied on supporting layer and is dried, to form the work of photoresist element on the supporting layer
Sequence.
2. according to the method described in claim 1, wherein, the film thickness after the drying of the blending liquid is 5 μm~50 μm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-161993 | 2012-07-20 | ||
| JP2012161993 | 2012-07-20 | ||
| PCT/JP2013/069650 WO2014014087A1 (en) | 2012-07-20 | 2013-07-19 | Method for producing photosensitive resin element |
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|---|---|
| CN104471482A CN104471482A (en) | 2015-03-25 |
| CN104471482B true CN104471482B (en) | 2019-08-02 |
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| JP (1) | JP6359452B2 (en) |
| KR (2) | KR101985992B1 (en) |
| CN (1) | CN104471482B (en) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0860742B1 (en) * | 1997-02-25 | 2001-04-04 | E.I. Du Pont De Nemours And Company | Flexible, flame-retardant, photoimageable composition for coating printing circuits |
| JP2006106287A (en) * | 2004-10-04 | 2006-04-20 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element and method for manufacturing photosensitive element |
| CN101142525A (en) * | 2005-02-09 | 2008-03-12 | 富士胶片株式会社 | Pattern formation material, pattern formation device, and pattern formation method |
| JP2011231156A (en) * | 2010-04-23 | 2011-11-17 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive resin varnish, photosensitive resin film, photosensitive resin cured product, and visible light light guide way |
| JP2012053229A (en) * | 2010-08-31 | 2012-03-15 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive resin varnish, photosensitive resin film, photosensitive resin cured product and light guide path for visible light |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11143069A (en) | 1997-11-10 | 1999-05-28 | Fuji Photo Film Co Ltd | Master plate for printed wiring |
| JP2002053621A (en) * | 2000-08-10 | 2002-02-19 | Asahi Kasei Corp | Photopolymerizable resin composition and laminate |
| JP4259855B2 (en) * | 2002-11-26 | 2009-04-30 | 旭化成エレクトロニクス株式会社 | Photosensitive resin composition |
| JP4966528B2 (en) | 2005-09-14 | 2012-07-04 | 旭化成イーマテリアルズ株式会社 | Pattern forming material, pattern forming apparatus and pattern forming method |
| JP2008003558A (en) * | 2006-05-26 | 2008-01-10 | Fujifilm Corp | Pattern forming material, pattern forming method and pattern |
| JP5476739B2 (en) * | 2008-07-30 | 2014-04-23 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method |
| JP2011209515A (en) * | 2010-03-30 | 2011-10-20 | Mitsubishi Paper Mills Ltd | Negative photosensitive lithographic printing plate |
-
2013
- 2013-07-19 MY MYPI2015000144A patent/MY180919A/en unknown
- 2013-07-19 CN CN201380038469.8A patent/CN104471482B/en active Active
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- 2013-07-19 KR KR1020157000527A patent/KR101985992B1/en active IP Right Grant
- 2013-07-19 JP JP2014525882A patent/JP6359452B2/en active Active
- 2013-07-19 KR KR1020177024431A patent/KR101986032B1/en active IP Right Grant
- 2013-07-19 WO PCT/JP2013/069650 patent/WO2014014087A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0860742B1 (en) * | 1997-02-25 | 2001-04-04 | E.I. Du Pont De Nemours And Company | Flexible, flame-retardant, photoimageable composition for coating printing circuits |
| JP2006106287A (en) * | 2004-10-04 | 2006-04-20 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element and method for manufacturing photosensitive element |
| CN101142525A (en) * | 2005-02-09 | 2008-03-12 | 富士胶片株式会社 | Pattern formation material, pattern formation device, and pattern formation method |
| JP2011231156A (en) * | 2010-04-23 | 2011-11-17 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive resin varnish, photosensitive resin film, photosensitive resin cured product, and visible light light guide way |
| JP2012053229A (en) * | 2010-08-31 | 2012-03-15 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive resin varnish, photosensitive resin film, photosensitive resin cured product and light guide path for visible light |
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| Publication number | Publication date |
|---|---|
| WO2014014087A1 (en) | 2014-01-23 |
| JPWO2014014087A1 (en) | 2016-07-07 |
| CN104471482A (en) | 2015-03-25 |
| JP6359452B2 (en) | 2018-07-18 |
| KR101986032B1 (en) | 2019-06-04 |
| KR20150029695A (en) | 2015-03-18 |
| KR101985992B1 (en) | 2019-06-04 |
| KR20170102582A (en) | 2017-09-11 |
| TW201405247A (en) | 2014-02-01 |
| TWI600969B (en) | 2017-10-01 |
| MY180919A (en) | 2020-12-12 |
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