KR20100082852A - Layered photosensitive-resin product - Google Patents
Layered photosensitive-resin product Download PDFInfo
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- KR20100082852A KR20100082852A KR1020107010522A KR20107010522A KR20100082852A KR 20100082852 A KR20100082852 A KR 20100082852A KR 1020107010522 A KR1020107010522 A KR 1020107010522A KR 20107010522 A KR20107010522 A KR 20107010522A KR 20100082852 A KR20100082852 A KR 20100082852A
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- photosensitive resin
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- resist pattern
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Materials For Photolithography (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
The present invention relates to a method of forming a resist pattern on a substrate using a photosensitive resin laminate obtained by laminating a photosensitive resin composition that can be developed with an alkaline aqueous solution on a support layer, the photosensitive resin laminate, and the use of the resist pattern. It is about. More specifically, manufacturing of printed wiring boards, manufacturing of flexible printed wiring boards, manufacturing of IC chip mounting lead frames (hereinafter referred to as lead frames), precision machining of metal foil such as metal mask manufacturing, BGA (ball grid array) or CSP Manufacture of semiconductor packages such as (chip size package), manufacture of tape substrates represented by TAB (Tape Automated Bonding) or COF (Chip On Film) The photosensitive resin composition which provides a resist pattern suitable for manufacture of a member, such as an ITO electrode, an address electrode, or an electromagnetic shield in the field of flat panel displays.
The conventional printed wiring board is manufactured by the photolithographic method. The photolithography method applies a photosensitive resin composition onto a substrate, performs pattern exposure, polymerizes and hardens the exposed portion of the photosensitive resin composition, removes the unexposed portion with a developer, forms a resist pattern on the substrate, and performs etching or plating treatment. After forming a conductor pattern, the resist pattern is peeled off from the board | substrate, and the method of forming a conductor pattern on a board | substrate is said.
In said photolithographic method, when apply | coating a photosensitive resin composition on a board | substrate, the method of apply | coating and drying a photoresist solution to a board | substrate, or the layer which consists of a support layer and the photosensitive resin composition (henceforth a "photosensitive resin layer" is also called. ) And the method of laminating | stacking the photosensitive resin laminated body (henceforth a "dry film resist") which laminated | stacked the protective layer sequentially according to necessity on a board | substrate. And in manufacture of a printed wiring board, the latter dry film resist is used in many cases.
The method of manufacturing a printed wiring board using said dry film resist is easily described below.
First, when a dry film resist has a protective layer, for example, a polyethylene film, it peels this from the photosensitive resin layer. Subsequently, using a laminator, a photosensitive resin layer and a support layer are laminated | stacked on a board | substrate, for example, a copper clad laminated board, in order of the board | substrate, the photosensitive resin layer, and a support layer. Subsequently, an exposure part is polymerized and hardened | cured by exposing the photosensitive resin layer to the ultraviolet-ray which contains the i line | wire (365 nm) which an ultrahigh pressure mercury lamp emits through the photomask which has a wiring pattern. The support layer, for example polyethylene terephthalate, is then peeled off. Subsequently, the unexposed part of the photosensitive resin layer is melt | dissolved or disperse | dissolved by the developing solution, for example, the aqueous solution which has weak alkalinity, and a resist pattern is formed on a board | substrate.
There are two methods for producing a metal conductor pattern using the resist pattern on the substrate thus formed, and there are two methods. A method of removing a metal part not covered with a resist by etching and attaching a metal by plating. There is a way to. In particular, in recent years, the former method is widely used in the simplicity of the process.
In the method of removing a metal part by etching, the metal in the hole is not etched by covering the through hole (through hole) of the substrate or the via hole for interlayer connection with a cured resist film. This method is called tenting method. In the etching step, for example, a cupric chloride, ferric chloride or copper ammonia complex solution is used.
With recent miniaturization of wiring intervals in printed wiring boards, high resolution and high tentability are required for dry film resists in order to manufacture narrow pitch patterns at a good production rate. As a method of increasing the resolution, the dry film resist can be increased simply by thinning, while the drag on the physical external force of the film due to the spraying of the developing process and the etching process is weakened. The problem was that the via hole could not be protected (the tentability was not good).
Patent document 1 has the indication of the outstanding photoresist by having many trifunctional monomers in the unsaturated compound in the photosensitive resin composition. However, it only describes the ratio of the trifunctional monomer in an unsaturated compound, and there existed a problem that tentability was not excellent in a certain range. About patent document 1, it mentions later in a comparative example.
Patent Literature 2 discloses an excellent photoresist with a tetrafunctional monomer as an unsaturated compound in the photosensitive resin composition. However, there existed a problem that tent property was not excellent in the direct drawing exposure using these.
Patent Document 3 discloses an excellent photoresist with a trifunctional monomer in an unsaturated compound in the photosensitive resin composition. However, there was a problem that the tentability was not excellent in the direct drawing exposure by the thin film using these.
However, when these polyfunctional monomers are contained in a large amount in the photosensitive resin composition, there also existed a problem that oily aggregates generate | occur | produce at the time of image development.
Therefore, also in direct drawing exposure, it was desired that tent property was favorable, that the aggregate at the time of image development is not oily, and there was also little powdery aggregate.
Even when the thickness of the photosensitive resin layer is thin to 3 to 15 µm, the photosensitive resin laminate has a good tentability even when exposed by direct drawing exposure, and no oily aggregates are generated at the time of development, and the powdery aggregates are also less. The purpose is to provide a sieve.
The said subject can be achieved by the following structure of this invention.
That is, this invention is as follows.
1. A photosensitive resin laminate formed by laminating at least a support layer and a photosensitive resin layer, the photosensitive resin layer comprising a photosensitive resin composition,
The photosensitive resin composition,
At least 25-64 mass% of (a) alkali-soluble resin,
(b) a compound having an unsaturated double bond capable of photopolymerization,
(c) 0.1-20 mass% of photoinitiators are contained,
Furthermore, the following (i), (ii) and (i) are satisfy | filled, The photosensitive resin laminated body characterized by the above-mentioned.
(Iii) at least one photopolymerizable unsaturated selected from the group consisting of a compound represented by the following general formula (I) and a compound represented by the following general formula (II) as a compound having a unsaturated double bond capable of photopolymerization (b) 30-55 mass% is contained with respect to the whole quantity of the photosensitive resin composition.
(Ii) The said (a) alkali-soluble resin has a weight average molecular weight of 70,000-220,000, and an acid equivalent of 100-600.
(Iii) The thickness of the photosensitive resin layer is 3-15 micrometers.
[Formula 1]
(In formula, R <1> , R <2> and R <3> are respectively independently H or CH <3> , n <1> , n <2> , n <3> and n <4> are the integers of 0-4 each independently, and may be 0 simultaneously. Is CH 3 or a group represented by OH)
[Formula 2]
(Wherein R 5 , R 6 , R 7 and R 8 are each independently H or CH 3 , and m 1 , m 2 , m 3 and m 4 are each independently an integer of 0 to 4, and may be 0 at the same time. do)
2. The compound (b) having at least one photopolymerizable unsaturated compound selected from the group consisting of a compound represented by the general formula (I) and a compound represented by the general formula (II) as a compound having an unsaturated double bond capable of photopolymerization. The photosensitive resin laminated body as described in said 1. containing 35-55 mass% with respect to the whole amount of the photosensitive resin composition.
3. (c) Photosensitive resin laminated body as described in said 1. or 2. whose photoinitiator is 9-phenylacridine.
4. When the ratio of the said (a) alkali-soluble resin with respect to the photosensitive resin composition whole quantity is A mass%, and the ratio of the compound which has the unsaturated double bond which can be photopolymerized (b) was made into B mass%, A / B is It is 1.1-1.3, The photosensitive resin laminated body in any one of said 1-3.
5. Resist pattern including the lamination process of laminating the photosensitive resin layer of the photosensitive resin laminated body in any one of said 1.-4 on a board | substrate, the exposure process which exposes an ultraviolet-ray, and the developing process which removes an unexposed part. Forming method.
6. Exposure in said exposure process WHEREIN: It exposes by direct drawing, The formation method of the resist pattern of the said 5. description characterized by the above-mentioned.
7. The manufacturing method of a conductor pattern including the process of etching or plating the board | substrate which formed the resist pattern by the method as described in said 5. or 6. using a copper clad laminated board as a board | substrate.
8. Manufacturing a printed wiring board using a metal-coated insulating plate as a substrate, etching or plating the substrate on which a resist pattern is formed by the method described in any one of 4. to 7. above, and peeling off the resist pattern. Way.
9. Using a metal plate as a substrate, etching the board | substrate which formed the resist pattern by the method in any one of said 4.-8., And peeling a resist pattern, The manufacturing method of the lead frame characterized by the above-mentioned.
10. A semiconductor, in which a substrate on which a resist pattern has been formed is plated by the method described in any one of 4. to 9. above using a wafer on which circuit formation as an LSI is completed, and the resist pattern is peeled off. Method of manufacture of the package.
11. A glass rib is used as a substrate, and the board | substrate which formed the resist pattern by the method in any one of said 4.-10. Is processed by the sandblasting method, and the uneven | corrugated pattern characterized by peeling a resist pattern The manufacturing method of the base material which has a.
Although the photosensitive resin laminated body of this invention is 3-15 micrometers in thickness, even if it is exposed by direct drawing exposure, tent property is favorable and oily aggregate at the time of image development does not generate | occur | produce. In addition, it has the effect that there is little powdery aggregate.
EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.
<Photosensitive resin laminated body>
The photosensitive resin laminated body of this invention is a photosensitive resin laminated body formed by laminating | stacking a support layer and the photosensitive resin layer at least, The photosensitive resin layer consists of a photosensitive resin composition,
The photosensitive resin composition,
At least 25-64 mass% of (a) alkali-soluble resin,
(b) a compound having an unsaturated double bond capable of photopolymerization,
(c) 0.1-20 mass% of photoinitiators are contained,
Furthermore, the following (i), (ii) and (i) are satisfy | filled, The photosensitive resin laminated body characterized by the above-mentioned.
(Iii) at least one photopolymerizable unsaturated selected from the group consisting of a compound represented by the following general formula (I) and a compound represented by the following general formula (II) as a compound having a unsaturated double bond capable of photopolymerization (b) 30-55 mass% is contained with respect to the whole quantity of the photosensitive resin composition.
(Ii) The said (a) alkali-soluble resin has a weight average molecular weight of 70,000-220,000, and an acid equivalent of 100-600.
(Iii) The thickness of the photosensitive resin layer is 3-15 micrometers.
(3)
(In formula, R <1> , R <2> and R <3> are respectively independently H or CH <3> , n <1> , n <2> , n <3> and n <4> are the integers of 0-4 each independently, and may be 0 simultaneously. Is CH 3 or a group represented by OH)
[Formula 4]
(Wherein R 5 , R 6 , R 7 and R 8 are each independently H or CH 3 , and m 1 , m 2 , m 3 and m 4 are each independently an integer of 0 to 4, and may be 0 at the same time. do)
When describing about the compounding quantity of each component in the photosensitive resin composition, the compounding quantity of each component is described in the mass% at the time of the solid content whole in the photosensitive resin composition.
(a) alkali-soluble resin
Alkali-soluble resin means vinyl resin containing a carboxyl group, For example, it is copolymers, such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, and (meth) acrylamide.
(a) Alkali-soluble resin contains a carboxyl group and it is preferable that acid equivalent is 100-600. An acid equivalent means the mass of the linear polymer which has 1 equivalent of carboxyl group in it. The acid equivalent is more preferably 250 or more and 450 or less. 100 or more are preferable at the point which image development resistance improves, a resolution and adhesiveness improve, and 600 or less are preferable at the point which developability and peelability improve. The acid equivalent is measured by potentiometric titration using a Hiranuma automatic titration device (COM-555) manufactured by Hiranuma Industries, Ltd., using 0.1 mol / L sodium hydroxide.
It is preferable that the weight average molecular weights of (a) alkali-soluble resin used for this invention are 70,000 or more and 220,000 or less. 220,000 or less are preferable at the point which developability improves. It is preferable that a weight average molecular weight is 70,000 or more from a tent property and aggregate property. More preferably, they are 70,000 or more and 200,000 or less. More preferably, they are 70,000 or more and 120,000 or less. The weight average molecular weight is gel permeation chromatography (GPC) manufactured by Nihon Spectroscopy Co., Ltd. (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko Co., Ltd.) (KF-807, KF -806M, KF-806M, KF-802.5) Four series, moving bed solvent: Tetrahydrofuran, polystyrene conversion by polystyrene standard sample (using calibration curve by Shodex STANDARD SM-105 manufactured by Showa Electric Co., Ltd.) Obtained as
It is preferable that alkali-soluble resin is a copolymer which consists of at least 1 type or more of the 1st monomer mentioned later and at least 1 type or more of the 2nd monomer mentioned later.
The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. For example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid semiester are mentioned. Especially, (meth) acrylic acid is preferable.
Here, (meth) acryl represents acryl and / or methacryl. It is the same below.
The second monomer is non-acidic and is a monomer having at least one polymerizable unsaturated group in the molecule. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth ) Acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylic Ester, ester of vinyl alcohol, For example, vinyl acetate, (meth) acrylonitrile, styrene, and a styrene derivative are mentioned. Especially, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable.
(a) Alkali-soluble resin contains a carboxyl group, acid equivalent is 100-600, and a weight average molecular weight is 70,000-220,000 is a preferable embodiment of this invention from a tent property and aggregate property.
The ratio with respect to the sum total of the photosensitive resin composition of (a) alkali-soluble resin is 25-64 mass%, Preferably it is 40-60 mass%. 25 mass% or more and 64 mass% or less are preferable from a viewpoint that the resist pattern formed by exposure and image development has sufficient tolerance in the characteristics as a resist, for example, tenting, an etching, and various plating processes.
(b) photopolymerizable unsaturated compounds
The unsaturated compound which can photopolymerize is a compound which has at least 1 ethylenically unsaturated bond in a molecule | numerator.
In the photosensitive resin composition of this invention, (b) At least 1 chosen from the group which consists of a compound represented by the following general formula (I) and a compound represented by the following general formula (II) as a compound which has unsaturated double bond which can be photopolymerized. 30-55 mass% of unsaturated photo-polymerizable unsaturated compounds are contained with respect to the whole quantity of the photosensitive resin composition.
[Chemical Formula 5]
(In formula, R <1> , R <2> and R <3> are respectively independently H or CH <3> , n <1> , n <2> , n <3> and n <4> are the integers of 0-4 each independently, and may be 0 simultaneously. Is CH 3 or a group represented by OH)
[Formula 6]
(Wherein R 5 , R 6 , R 7 and R 8 are each independently H or CH 3 , and m 1 , m 2 , m 3 and m 4 are each independently an integer of 0 to 4, and may be 0 at the same time. do)
As a specific example of the at least 1 sort (s) of photopolymerizable unsaturated compound chosen from the group which consists of a compound represented by the said General formula (I) and the compound represented by the said General formula (II), it is the following in general formula (I), for example. Wherein R 1 , R 2 and R 3 are H, n 1 , n 2 and n 3 are integers of 1, n 4 is an integer of 0, and W is CH 3 (Shin-Nakamura Chemical Co., Ltd.) NK ester A-TMPT-3PO) manufactured by the company, and in the above general formula (I), R 1 , R 2 and R 3 are H, n 1 , n 2 and n 3 are integers of 3, n 4 is an integer of 0, W may be a CH 3 the compound (produced by Shin-Nakamura chemical Co. (Note) NK ester a-TMPT-9PO of company) and the like. In addition, in the said General formula (II), R <5> , R <6> , R <7> and R <8> are H, and m <1> , m <2> , m <3> and m <4> are integers of 0 (Shin-Nakamura Chemical Co., Ltd.) NK ester A-TMMT) manufactured by the company, and in the general formula (II), R 5 , R 6 , R 7 and R 8 are H, and m 1 , m 2 , m 3 and m 4 are 1; A compound (SR-494 manufactured by Satoma Japan Co., Ltd.) which is an integer is mentioned.
Content of at least 1 sort (s) of photopolymerizable unsaturated compound chosen from the group which consists of a compound represented by the said General formula (I) and the compound represented by the said General formula (II) is 35-55 mass% from a tentability viewpoint, More preferably, Is 40-55 mass%. In addition, in addition to the compound represented by the said General formula (I) and the said General formula (II), the unsaturated compound which can be photopolymerized can be used for (b) unsaturated compound which can be photopolymerized. For example, 1, 6- hexanediol di (meth) acrylate, 1, 4- cyclohexanediol di (meth) acrylate, polyethyleneglycol di (meth) acrylate, 2-di (p-hydroxyphenyl) Propanedi (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropanetriacrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropanetriglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, β- Hydroxypropyl-β '-(acryloyloxy) propyl phthalate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxypolyal Alkylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate.
Moreover, a urethane compound is also mentioned. As a urethane compound, For example, hexamethylene diisocyanate, tolylene diisocyanate, or a diisocyanate compound, for example, 2,2,4-trimethylhexamethylene diisocyanate, a hydroxyl group (meth) acryl in 1 molecule The urethane compound of the compound which has group, for example, 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate is mentioned. Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by Nippon Oil-based Co., Ltd., Blemmer PP1000). These may be used independently and may use two or more types together.
(B) Photopolymerizable unsaturated double bonds containing at least one photopolymerizable unsaturated compound selected from the group consisting of a compound represented by the general formula (I) and a compound represented by the general formula (II) Content is 30-55 mass% with respect to the whole quantity of the photosensitive resin composition, and 35 mass%-55 mass% are preferable. More preferably, it is 40-55 mass%.
In addition, when the ratio of the said (a) alkali-soluble resin with respect to the photosensitive resin composition whole quantity is A mass%, and the ratio of the compound which has the unsaturated double bond which can be photopolymerized (b) was made into B mass%, A / B is It is preferable embodiment of this invention that it is 1.1-1.3. It is preferable that A / B is 1.1 or more from a viewpoint of tent property, and it is preferable that A / B is 1.3 or less.
(c) photopolymerization initiator
As photosensitive resin composition, what is generally known can be used as (c) photoinitiator. The amount of the (c) photoinitiator contained in the photosensitive resin composition is 0.1-20 mass%, and a more preferable range is 0.5-10 mass%. 0.1 mass% or more is preferable from a viewpoint of obtaining sufficient sensitivity, and 20 mass% or less is preferable from a viewpoint of fully permeating light to a resist bottom surface, and obtaining favorable high resolution.
As such a photoinitiator, 2-ethyl anthraquinone, an octaethyl anthraquinone, a 1, 2- benzanthhraquinone, a 2, 3- benzanthhraquinone, 2-phenyl anthraquinone, 2, 3- diphenyl anthraquinone, 1 -Chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenan Quinones such as traquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone and 3-chloro-2-methylanthraquinone, aromatic ketones such as benzophenone and Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, benzoin or benzoin ethers such as benzoin, benzoin ethyl ether, benzo Inphenyl ether, methyl benzoin, ethyl benzoin, dialkyl ketals, for example benzyl dimethyl ketal, benzyl diethyl ketal, thioxanthones, for example, diethyl thioxanthone, chlorthioxanthone, di To alkylaminobenzoic acid Esters such as ethyl dimethylaminobenzoate and oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione 2- (O-ethoxycarbonyl) oxime, ropin dimer, for example 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-chlorophenyl)- 4,5-bis- (m-methoxyphenyl) imidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, acridine compound, for example, 9-phenylacridine. These compounds may be used independently and may use two or more types together. An acridine compound is preferable at the point which can improve tent property and can suppress generation | occurrence | production of an oily aggregate, and 9-phenyl acridine is especially preferable. The oily aggregate here refers to a highly viscous aggregate and is considered to be composed mainly of a compound having an unsaturated double bond. On the other hand, the powdery aggregate is considered to have a inhibitor and initiator as a main component, and is different from the oily aggregate.
(d) other ingredients
In order to improve the handleability of the photosensitive resin composition in this invention, you may add a leuco dye, a fluorane dye, or a coloring substance.
Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green]. Especially, when leuco crystal violet is used, contrast is favorable and preferable. It is preferable to contain 0.1-10 mass% of content in the case of containing leuco dye in the photosensitive resin composition. 0.1 mass% or more is preferable from a viewpoint of contrast expression, and 10 mass% or less is preferable from a viewpoint of maintenance of storage stability.
The use of a leuco dye and the following halogen compound in combination in the photosensitive resin composition is a preferred embodiment of the present invention in view of adhesion and contrast.
As a coloring substance, fuchsin, phthalocyanine green, auramin base, paramagenta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green (Hodogaya Chemical Co., Ltd. make) Trademark) MALACHITE GREEN), basic blue 20, and diamond green (Eisen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). It is preferable to contain 0.001-1 mass% of addition amount in the case of containing a coloring substance in the photosensitive resin composition. The content of 0.001 mass% or more has the effect of improving handleability, and the content of 1 mass% or less has the effect of maintaining storage stability.
In the photosensitive resin composition of this invention, N-aryl- from a viewpoint of a sensitivity
The photosensitive resin composition of this invention may contain a halogen compound. As a halogen compound, for example, amyl bromide, isoamyl bromide, isobutyl bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, and tris (2,3) Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, and trichlorazine compounds. Among them, tribromomethylphenyl sulfone is particularly preferably used. Content in the case of containing a halogen compound is 0.01-3 mass% in the photosensitive resin composition.
Furthermore, in order to improve the thermal stability and the storage stability of the photosensitive resin composition of this invention, at least 1 sort (s) of compound chosen from the group which consists of a radical polymerization inhibitor, benzotriazoles, and carboxy benzotriazoles is added to the photosensitive resin composition. It may be.
Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p- Cresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt And diphenylnitrosoamine.
As benzotriazoles, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole and bis (N-2-ethylhexyl) aminomethylene-1,2 , 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotria Sol.
Moreover, as carboxy benzotriazoles, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di-2), for example -Ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxy Benzotriazole is mentioned.
Preferably the total addition amount of a radical polymerization inhibitor, benzotriazoles, and carboxy benzotriazoles is 0.01-3 mass%, More preferably, it is 0.05-1 mass%. 0.01 mass% or more is preferable from a viewpoint of providing storage stability to the photosensitive resin composition, and 3 mass% or less is more preferable from a viewpoint of maintaining a sensitivity.
The photosensitive resin composition of this invention may contain a plasticizer as needed. As such additives, for example, polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, poly Glycol esters such as oxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluene sulfonic acid amide, p-toluene sulfonic acid amide, Tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri-n-propyl and acetyl citrate tri-n-butyl.
As content of a plasticizer, it is preferable to contain 5-50 mass% in the photosensitive resin composition, More preferably, it is 5-30 mass%. 5 mass% or more is preferable from a viewpoint of suppressing the delay of image development time, and providing flexibility to a cured film, and 50 mass% or less is preferable from a viewpoint of suppressing hardening shortage or cold flow.
The photosensitive resin laminated body of this invention contains the photosensitive resin layer and support layer which consist of a photosensitive resin composition. As needed, you may have a protective layer on the surface on the opposite side to the support layer side of the photosensitive resin layer. As a support layer used here, the transparent thing which permeate | transmits the light radiated | emitted from an exposure light source is preferable. As such a support layer, for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer A film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film is mentioned. These films can also be stretched as needed. It is preferable that haze is five or less. Although the thickness of the film is advantageous in terms of image formation and economical efficiency, it is preferably 10 to 30 µm in order to maintain the strength.
In addition, an important characteristic of the protective layer used for the photosensitive resin laminate is that the protective layer is smaller than the supporting layer in terms of adhesion to the photosensitive resin layer and can be easily peeled off. For example, a polyethylene film and a polypropylene film can be used suitably as a protective layer. Moreover, the film excellent in the peelability disclosed in Unexamined-Japanese-Patent No. 59-202457 can be used. 10-100 micrometers is preferable and, as for the film thickness of a protective layer, 10-50 micrometers is more preferable. Although the thickness of the photosensitive resin layer in a photosensitive resin laminated body differs in a use, Preferably it is 5-100 micrometers, More preferably, it is 7-60 micrometers, The thinner, the resolution improves, and the thicker, the film strength is Is improved.
As a method of manufacturing the photosensitive resin laminated body of this invention by laminating | stacking a support layer, the photosensitive resin layer, and a protective layer sequentially as needed, the method known conventionally can be employ | adopted. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with the solvent which melt | dissolves them, it is made into a uniform solution, it is first apply | coated and dried using a bar coater or a roll coater on a support layer, and the photosensitive resin composition on a support layer The photosensitive resin layer which consists of is laminated | stacked. Then, the photosensitive resin laminated body can be manufactured by laminating a protective layer on the photosensitive resin layer as needed.
As said solvent, ketones represented by methyl ethyl ketone (MEK) and alcohols represented by methanol, ethanol and isopropanol are mentioned. It is preferable to add to the photosensitive resin composition so that the viscosity of the photosensitive resin composition solution apply | coated on a support layer may be 500-4000 mPa at 25 degreeC.
<Resist Pattern Forming Method>
The resist pattern using the photosensitive resin laminated body of this invention can be formed by the process including a lamination process, an exposure process, and a developing process. An example of the specific method is shown below.
As the substrate to be processed, a copper clad laminate is used for the purpose of manufacturing a printed wiring board, and a glass substrate such as a substrate for a plasma display panel, a surface electrolytic display substrate, an organic EL sealing cap, or a through hole is used for the purpose of manufacturing the uneven substrate. The formed silicon wafer and the ceramic base material are mentioned. Plasma display base material is a base material which formed an electrode on glass, apply | coated a dielectric layer, apply | coated the partition glass paste, and sand blasted the partition glass paste part, and formed the partition. The sand-blasted process of these to-be-processed base materials turns into an uneven base material.
First, the lamination process is performed using a laminator. When the photosensitive resin laminated body has a protective layer, after peeling a protective layer, a photosensitive resin layer is heat-compressed and laminated | stacked on the surface of a to-be-processed base material with a laminator. In this case, the photosensitive resin layer may be laminated only on one surface of the substrate surface or may be laminated on both surfaces. The heating temperature at this time is generally 40-160 degreeC. In addition, the adhesion and chemical resistance are improved by performing the heat pressing twice or more. At this time, crimping | bonding may use the two-stage laminator provided with two rolls, and may make it crimp by passing through a roll several times.
Next, an exposure process is performed using an exposure machine. If necessary, the support is peeled off, passed through a photomask, and exposed with actinic light. The exposure amount is determined in accordance with the light source illuminance and the exposure time. You may measure using a photometer.
Moreover, in an exposure process, you may use the direct drawing exposure method. Direct drawing exposure is a system which draws and exposes directly on a board | substrate, without using a photomask. As the light source, for example, a semiconductor laser having a wavelength of 350 to 410 nm or an ultrahigh pressure mercury lamp is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined according to the illuminance of the light source and the moving speed of the substrate.
Next, a developing process is performed using a developing apparatus. When a support exists on the photosensitive resin layer after exposure, it removes as needed and then develops and removes an unexposed part using the developing solution of aqueous alkali solution, and obtains a resist image. As the aqueous alkali solution, an aqueous solution of Na 2 CO 3 or K 2 CO 3 is used. They are selected according to the properties of the photosensitive resin layer, and is generally an aqueous solution of Na 2 CO 3 concentration of 0.2 to 2 mass%, 20 ~ 40 ℃. In the alkaline aqueous solution, a small amount of an organic solvent for promoting the surface active agent, the antifoaming agent and the development may be mixed.
Although a resist pattern is obtained by the above-mentioned process, in some cases, the heating process of 100-300 degreeC can also be performed further. By performing this heating process, further chemical-resistant improvement is attained. For heating, hot air, infrared or far-infrared furnaces are used.
<Manufacturing method of a conductor pattern, manufacturing method of a printed wiring board>
The manufacturing method of the printed wiring board of this invention is performed by following the following processes following the resist pattern formation method mentioned above using the copper clad laminated board and the flexible substrate as a board | substrate.
First, the copper surface of the substrate exposed by development is formed using a known method such as etching or plating.
Then, a resist pattern is peeled from a board | substrate with the aqueous solution which has stronger alkalinity than a developing solution, and a desired printed wiring board is obtained. Although there is no restriction | limiting in particular also about the aqueous alkali solution for peeling (henceforth "a peeling liquid"), The aqueous solution of NaOH and KOH with a density | concentration of 2-5 mass% and a temperature of 40-70 degreeC is generally used. A small amount of water-soluble solvent can also be added to the stripping solution.
<Production method of the lead frame>
The manufacturing method of the lead frame of this invention is performed by following the following process following the formation method of the resist pattern mentioned above using the metal plate, for example, copper, a copper alloy, an iron type alloy as a board | substrate.
First, the substrate exposed by development is etched to form a conductor pattern. Thereafter, the resist pattern is peeled off in the same manner as the method for producing a printed wiring board described above to obtain a desired lead frame.
<Method of Manufacturing Semiconductor Package>
The manufacturing method of the semiconductor package of this invention is performed by following the following process following the formation method of the resist pattern mentioned above using the wafer in which the circuit formation as LSI was complete | finished.
First, columnar plating with copper or solder is applied to the opening exposed by development to form a conductor pattern. Then, a resist pattern is peeled off by the method similar to the manufacturing method of the above-mentioned printed wiring board, and a desired semiconductor package is obtained by further removing the thin metal layer of parts other than columnar plating by etching.
Example
The present invention will be described based on examples.
Below, the manufacturing method of the sample for evaluation of an Example and a comparative example, the evaluation method, and the evaluation result about the obtained sample are shown.
1) Preparation of Sample for Evaluation
The photosensitive resin laminated body in an Example and a comparative example was manufactured as follows.
<Production of Photosensitive Resin Laminate>
The solution of the composition shown in Table 1 was prepared so that solid content might be 50 mass%, and it stirred well and mixed, and it was shown in Table 1 on the polyethylene terephthalate film (R340-G16 by Mitsubishi Chemical Corporation) of 16 micrometer thickness as a support film. The photosensitive resin composition shown was apply | coated uniformly using the blade coater, and it dried at 95 degreeC for 1 minute. The film thickness of the photosensitive resin layer after drying was 10 micrometers. Subsequently, a 35 micrometer-thick polyethylene film (GF-858 by Tama Poly) was adhered as a protective layer on the surface on the photosensitive resin layer, and the photosensitive resin laminated body was obtained.
<Substrate>
It evaluated using the 0.4 mm-thick copper clad laminated board which laminated | stacked 35 micrometer copper foil on insulating resin. In addition, when using another board | substrate, such content was described.
<Laminate>
It laminated at the roll temperature of 105 degreeC with the hot roll laminator (Al-700 by Asahi Chemical Engineering Co., Ltd.), peeling the protective layer of the photosensitive resin laminated body of this invention. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m / min.
<Exposure>
The photosensitive resin layer was exposed at the exposure amount of 12 mJ / cm <2> by 8 W by the direct drawing exposure machine (Zoragon9000 by Orbotech Co., Ltd.).
<Phenomena>
A 1.0 mass% Na 2 CO 3 aqueous solution at 30 ° C. was sprayed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin layer. The actual developing time was developed for 24 seconds, and the washing time was washed with 36 seconds.
2) Evaluation method
In addition to the method described in Preparation of the above-mentioned evaluation sample, each performance was evaluated by the following method.
<Tent property>
The substrate laminated | stacked on both surfaces by the said method to the 500 mm x 500 mm 0.2 mm-thick copper clad laminated board manufactured by 2500 through-holes of 0.3 mm diameter is directly exposed to the whole surface by the said exposure method. To obtain a cured film, and developed by the above-described developing method. The number which the cured film was torn after image development was counted, and it classified into ranks as follows.
◎: 25 pieces or less
(Circle): The number of torn exceeds 25 pieces, and 75 pieces or less
X: The number torn exceeds 75 pieces.
<Occurrence of oily aggregates>
Only 2.4 m <2> of photosensitive resin layers of the photosensitive resin laminated body were immersed in 200 ml developing solution, and it stirred for 2 hours and made it melt | dissolve at 30 degreeC. Thereafter, the mixture was left to stand and classified as follows according to the solution state after 72 hours.
(Circle): Oily aggregate and powdery aggregate do not generate | occur | produce.
(Triangle | delta): There are few oily aggregates and powdery aggregates.
X: There are many oily aggregates and powdery aggregates.
<Peel Strength of Support Layer (PET)>
After preparing the board | substrate which laminated the photosensitive resin layer of the photosensitive resin laminated body on the single side | surface by the said method, and leaving it to stand at 23 degreeC and 50% relative humidity for 24 hours, 1-inch-wide support layer (here PET) is peeled 180 degrees. The strength was measured by Tensilon RTM-500 (manufactured by Toyo Seiki Co., Ltd.) and rank classification was performed as follows.
(Circle): The maximum average value of peeling strength is 3 gf or more.
(Triangle | delta): The maximum average value of peeling strength is less than 3 gf.
3) Evaluation result
Table 1 shows the evaluation results of the examples and the comparative examples. The mass part of B-1-B-4 in Table 1 is a mass part of solid content, and does not contain a solvent. In order to prepare the photosensitive resin composition, the methyl ethyl ketone solution of 50 mass% of solid content concentration of B-1-B-4 was prepared previously, and the solution of each B-1-B-4 was mix | blended so that it might become solid content of Table 1.
<Symbol explanation>
B-1: 25 mass% of methacrylic acid, 65 mass% of methyl methacrylate, and 10 mass% of butyl acrylate (weight average molecular weight 100,000, acid equivalent 344)
B-2: ternary copolymer of 25% by mass of methacrylic acid, 65% by mass of methyl methacrylate, and 10% by mass of butyl acrylate (weight average molecular weight 200,000, acid equivalent 370)
B-3: 25 mass% of methacrylic acid, 50 mass% of methyl methacrylate, 25 mass% of styrene copolymers (weight average molecular weight 50,000, acid equivalent 344)
B-4: 25 mass% of methacrylic acid, 50 mass% of methyl methacrylate, 25 mass% of butyl acrylate (weight average molecular weight 70,000, acid equivalent 344)
B-5: 80 mass% of benzyl methacrylate, the binary copolymer of 20 mass% of methacrylic acid (weight average molecular weight 100,000, acid equivalent 430)
M-1: tetraacrylate which added 1 mol of ethylene oxide to four terminal of pentaerythritol, respectively (SR-494 by Satoma Japan Co., Ltd.)
M-2: tetraacrylate which acrylated four terminals of pentaerythritol
M-3: Triacrylate which added an average of 3 mol ethylene oxide to trimethylolpropane (A-TMPT-3EO by Shin-Nakamura Chemical)
M-4: triacrylate which added an average of 3 mol of propylene oxide to trimethylolpropane
M-5: dimethacrylate of polyethylene glycol in which an average of 2 mol of ethylene oxide was added to the sock end of bisphenol A, respectively
M-6: Polypropylene Glycol Diacrylate
I-1: 9-phenylacridine
I-2: N-phenylglycine
I-3: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer
I-4: 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline
I-5: 2- (o-chlorophenyl) -4,5-bis- (m-methoxyphenyl) imidazole dimer
D-1: diamond green
D-2: leuco crystal violet
F-1: methyl ethyl ketone
In Comparative Example 1, when a polymer having a weight average molecular weight of less than 70,000 was used as the alkali-soluble resin, an oily aggregate was generated at the time of development and a problem occurred.
In the comparative example 2, the ratio of the compound represented by the said General formula (II) in the photosensitive resin composition was less than 30 mass%, and the tent property fell.
In the comparative example 3, the ratio of the compound represented by the said general formula (II) in the photosensitive resin composition is more than 55 mass%, and the ratio of said (a) alkali-soluble resin with respect to the whole amount of photosensitive resin composition is A mass%, When the ratio of the compound (b) having a unsaturated double bond capable of photopolymerization was B mass%, A / B was less than 1.1, resulting in deterioration of the tentability. The comparative example 4 is a follow-up of Unexamined-Japanese-Patent No. 11-119422. In the comparative example 4, since the polyfunctional photopolymerizable unsaturated compound which does not correspond to the compound represented by the said General formula (I) and the compound represented by the said General formula (II) was not used, tent property deteriorates and an oily aggregate is bad. This result was generated.
Since the photosensitive resin laminated body of this invention protects a through hole from an alkaline developing solution and an etching solution by exposing on the laminated board | substrate, since the following process can be simplified and since there is little oily aggregate in a developing solution, cleaning of an apparatus is carried out. In addition to this, it is useful for the production of printed circuit boards by alkali development.
Claims (11)
The photosensitive resin composition,
At least 25-64 mass% of (a) alkali-soluble resin,
(b) a compound having an unsaturated double bond capable of photopolymerization,
(c) 0.1-20 mass% of photoinitiators are contained,
Furthermore, the following (i), (ii) and (i) are satisfy | filled, The photosensitive resin laminated body characterized by the above-mentioned.
(Iii) at least one photopolymerizable unsaturated selected from the group consisting of a compound represented by the following general formula (I) and a compound represented by the following general formula (II) as a compound having a unsaturated double bond capable of photopolymerization (b) 30-55 mass% is contained with respect to the whole quantity of the photosensitive resin composition.
(Ii) The said (a) alkali-soluble resin has a weight average molecular weight of 70,000-220,000, and an acid equivalent of 100-600.
(Iii) The thickness of the photosensitive resin layer is 3-15 micrometers.
[Formula 1]
(In formula, R <1> , R <2> and R <3> are respectively independently H or CH <3> , n <1> , n <2> , n <3> and n <4> are the integers of 0-4 each independently, and may be 0 simultaneously. Is CH 3 or a group represented by OH)
(2)
(Wherein R 5 , R 6 , R 7 and R 8 are each independently H or CH 3 , and m 1 , m 2 , m 3 and m 4 are each independently an integer of 0 to 4, and may be 0 at the same time. do)
As the compound (b) having a unsaturated double bond capable of photopolymerization, at least one photopolymerizable unsaturated compound selected from the group consisting of a compound represented by the general formula (I) and a compound represented by the general formula (II), The photosensitive resin laminated body containing 35-55 mass% with respect to the whole amount of the photosensitive resin composition.
(c) Photosensitive resin laminated body whose photoinitiator is 9-phenylacridine.
A / B is 1.1- when the ratio of the said (a) alkali-soluble resin with respect to the photosensitive resin composition whole quantity is A mass%, and the ratio of the compound (b) which has a unsaturated double bond which can be photopolymerized is B mass%. It is 1.3, The photosensitive resin laminated body.
The exposure process WHEREIN: It exposes by direct drawing, The formation method of the resist pattern characterized by the above-mentioned.
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| KR (1) | KR101207242B1 (en) |
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| TWI424269B (en) * | 2011-01-25 | 2014-01-21 | Chunghwa Picture Tubes Ltd | Hydrophilic monomer, hydrophilic photoresist composition containing the same, and resist pattern formation method |
| JP5990366B2 (en) * | 2011-03-31 | 2016-09-14 | 旭化成株式会社 | Laminated body and roll using the same |
| JP2012215787A (en) * | 2011-04-01 | 2012-11-08 | Hitachi Chem Co Ltd | Photosensitive resin composition, photosensitive element, method for manufacturing resist pattern, and printed wiring board and method for manufacturing the same |
| CN103064253B (en) * | 2012-12-05 | 2015-04-08 | 北京化工大学常州先进材料研究院 | Photosensitive composition containing acridine oxide |
| CN111694218B (en) * | 2014-05-21 | 2023-09-08 | 旭化成株式会社 | Photosensitive resin composition and method for forming circuit pattern |
| TWI620017B (en) * | 2015-04-08 | 2018-04-01 | Asahi Chemical Ind | Photosensitive resin composition |
| CN114609864A (en) * | 2016-12-05 | 2022-06-10 | 旭化成株式会社 | Photosensitive resin composition |
| US20230375930A1 (en) * | 2020-10-23 | 2023-11-23 | Asahi Kasei Kabushiki Kaisha | Photosensitive resin multilayer body |
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| JPS6424247A (en) * | 1987-07-21 | 1989-01-26 | Hitachi Chemical Co Ltd | Photosensitive resin composition |
| JPS6425147A (en) * | 1987-07-22 | 1989-01-27 | Hitachi Chemical Co Ltd | Photosensitive resin composition |
| JPH06214400A (en) * | 1993-01-18 | 1994-08-05 | Sekisui Chem Co Ltd | Production of image display board |
| JP3100039B2 (en) * | 1997-07-04 | 2000-10-16 | 日本合成化学工業株式会社 | Dry film resist for tenting |
| JP2000344812A (en) * | 1999-06-07 | 2000-12-12 | Toyo Ink Mfg Co Ltd | Polymerizable composition |
| JP4609824B2 (en) * | 2001-07-02 | 2011-01-12 | 太陽ホールディングス株式会社 | Photosensitive resin composition |
| JP2004037518A (en) * | 2002-06-28 | 2004-02-05 | Hitachi Chem Co Ltd | Surface irregularities forming method, optical film obtained thereby and diffuse reflector plate and manufacture method for diffuse reflector plate |
| JP2004198993A (en) * | 2002-12-20 | 2004-07-15 | Hitachi Chem Co Ltd | Energy-sensitive negative resin composition and photosensitive element used for organic layer having roughened surface for liquid crystal display device |
| TW200622486A (en) * | 2004-10-14 | 2006-07-01 | Sumitomo Chemical Co | Radiation sensitive resin composition |
| TWI377440B (en) * | 2004-10-14 | 2012-11-21 | Sumitomo Chemical Co | Radiation sensitive resin composition |
| CN1896872A (en) * | 2005-07-12 | 2007-01-17 | 富士胶片电子材料有限公司 | Photo setting composition, color filter and its preparation method |
| JP4761909B2 (en) * | 2005-10-05 | 2011-08-31 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition and laminate |
| JP4697031B2 (en) * | 2006-04-21 | 2011-06-08 | Ｊｓｒ株式会社 | Inorganic particle-containing photosensitive resin composition, photosensitive film, and inorganic pattern forming method |
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| JPWO2009081925A1 (en) | 2011-05-06 |
| KR101207242B1 (en) | 2012-12-03 |
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| CN101910943B (en) | 2015-03-25 |
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