CN107926124A - Method for manufacturing insulating layer and multilayer board - Google Patents
Method for manufacturing insulating layer and multilayer board Download PDFInfo
- Publication number
- CN107926124A CN107926124A CN201780002758.0A CN201780002758A CN107926124A CN 107926124 A CN107926124 A CN 107926124A CN 201780002758 A CN201780002758 A CN 201780002758A CN 107926124 A CN107926124 A CN 107926124A
- Authority
- CN
- China
- Prior art keywords
- insulating layer
- layer
- metal layer
- carrier film
- chemical formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 72
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- 229910052751 metal Inorganic materials 0.000 claims description 161
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- OETHQSJEHLVLGH-UHFFFAOYSA-N metformin hydrochloride Chemical compound Cl.CN(C)C(=N)N=C(N)N OETHQSJEHLVLGH-UHFFFAOYSA-N 0.000 description 1
- AJBQAIDJQOJYFQ-UHFFFAOYSA-N methane;pyrrole-2,5-dione Chemical compound C.O=C1NC(=O)C=C1.O=C1NC(=O)C=C1 AJBQAIDJQOJYFQ-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- JAOPKYRWYXCGOQ-UHFFFAOYSA-N n,n-dimethyl-1-(4-methylphenyl)methanamine Chemical compound CN(C)CC1=CC=C(C)C=C1 JAOPKYRWYXCGOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical class C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4664—Adding a circuit layer by thick film methods, e.g. printing techniques or by other techniques for making conductive patterns by using pastes, inks or powders
- H05K3/4667—Adding a circuit layer by thick film methods, e.g. printing techniques or by other techniques for making conductive patterns by using pastes, inks or powders characterized by using an inorganic intermediate insulating layer
-
- 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
-
- 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
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- 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
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0023—Etching of the substrate by chemical or physical means by exposure and development of a photosensitive insulating layer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
-
- 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
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
- H05K3/4676—Single layer compositions
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to the method for manufacturing insulating layer, it can realize uniform and fine pattern while the efficiency in terms of improving cost and productivity, and may also be ensured that excellent mechanical property；And manufacture the method for multilayer board using the insulating layer obtained by the method for manufacture insulating layer.
Description
Technical field
Cross reference to related applications
This application claims based on the korean patent application 10- submitted for 9th in August in 2016 to Korean Intellectual Property Office
No. 2016-0101419 and the rights and interests on the July 28th, 2017 of the korean patent application submitted the 10-2017-0096355th, its
Disclosure is incorporated herein by reference in their entirety.
The present invention relates to for manufacturing the method for insulating layer and method for manufacturing multilayer board.More specifically
Ground, the present invention relates to the method for manufacturing insulating layer, it can be real while the efficiency in terms of improving cost and productivity
Now uniform and fine pattern, and may also be ensured that excellent mechanical property；And use the side by the manufacture insulating layer
The insulating layer that method obtains manufactures the method for multilayer board.
Background technology
Nearest electronic device increasingly minimizes, lightweight and multifunction.For this reason, with lamination PCB, (lamination prints
Circuit board) application field mainly expand rapidly in miniature device, the use of multilayer board increases sharply.
Multilayer board can carry out three dimensional wiring by plane routing.Especially in industrial electronic field, multilayer
Printed circuit board (PCB) improves the integrated level of function element such as integrated circuit (IC) and large scale integrated circuit (LSI), and still
Be conducive to miniaturization, lightweight, multifunction, the integrated of structure Electricity Functional part, installation time shortening and the cost of electronic device
The product of reduction etc..
The lamination PCB used in these application fields necessarily be formed the through hole for the connection between each layer.Through hole pair
Should be in the interlayer electrical communication path of multilayer board.In the past, through hole is process with power auger machinery, but with hole
Diameter diminishes due to the micro Process of circuit, due to the limit of processing cost increase and pore mechanical processing as caused by machine drilling
System, alternatively, there is laser processing.
In the case of laser processing, CO is used2Or YAG laser drillings.However, since the size of through hole is by laser drilling
Determine, for example, in CO2In the case of laser drilling, there is the limitation for the through hole for being difficult to manufacture a diameter of 40 μm or smaller.In addition,
Also there is the very big limitation of cost burden when necessarily be formed a large amount of through holes.
Therefore, it is proposed to the method for forming the through hole with thin diameter with low cost using photosensitive insulating material is upper to replace
State laser processing technology.Specifically, as photosensitive insulating material, it can be mentioned that thin patterns of openings can be formed using light sensitivity
The photosensitive insulating film for being referred to as " solder resist ".
Such photosensitive insulating material or solder resist are segmented into using the situation of sodium carbonate developers and use in addition
The situation of developer is to form pattern.Using in the case of other developer, photosensitive insulating material or solder resist have by
The limitation of real process is dfficult to apply in environment and cost reason.
On the other hand, when using sodium carbonate developers when, there are it is environmental-friendly the advantages of.In this case, in order to assign
Light sensitivity is given, using the sour modified acrylic ester resin containing big quantity carboxylic acid and acrylic acid groups, but due to most of propylene
Acid esters group is connected with carboxyl by ester bond, so comprising polymerization inhibitor etc. to be polymerize in the form of favourable, and also include light
Initiator etc. causes radical reaction will pass through ultraviolet light.
However, polymerization inhibitor, photoinitiator etc. may be diffused into outside resin under the high temperature conditions, so as in semiconductor
Cause the interfacial separation between insulating layer and conductive layer during and after encapsulation process.In addition, the ester bond in resin is in high humility
Under cause hydrolysis and reduce the crosslink density of resin, this causes the hydroscopicity of resin to increase.When hydroscopicity as described above compared with
Gao Shi, polymerization inhibitor, photoinitiator etc. be transformed under the high temperature conditions outside resin and during semiconductor package process and it
Cause the interfacial separation between insulating layer and conductive layer afterwards, and there are the limitation of HAST deterioration in characteristics.
Therefore, it is necessary to develop such method for being used to manufacture insulating layer：It is being prevented between insulating layer and conductive layer
Can be to be realized with a low cost uniform and fine pattern while interfacial separation.
The content of the invention
Technical problem
It is an object of the present invention to provide the method for manufacturing insulating layer, it is in terms of cost and productivity is improved
Uniform and fine pattern can be realized while efficiency, and may also be ensured that excellent mechanical property.
It is a further object to provide the insulating layer obtained using the method by the manufacture insulating layer to manufacture
The method of multilayer board.
Technical solution
One embodiment of the invention provides the method for manufacturing insulating layer, it comprises the following steps：By one
The opposed surface that the metal layer of carrier film is stained with a surface is adhered to comprising alkali soluble resins and thermal curable binding agent
In polymer resins layers；Patterned photosensitive resin layer is formed in the carrier film；Remove by the patterned photosensitive tree
The carrier film of lipid layer exposure and the metal layer are to form patterned metal layer；Divide from the patterned metal layer
From and remove the carrier film；
Make by the polymer resins layers alkali development of the patterned metal layer exposure；And the alkali development it
After make the polymer resins layers heat cure.
Another embodiment of the invention provides the method for manufacturing multilayer board, it is included in by institute
State and form the step of forming figuratum metal base thereon on the insulating layer of the method acquisition of manufacture insulating layer.
The method and use that are used to manufacture insulating layer of specific embodiment according to the present invention will be described in further detail below
In the method for manufacture multilayer board.
In the present specification, the example of halogen group includes fluorine, chlorine, bromine and iodine.
In the present specification, alkyl can be linear or branched, and carbon number is not particularly limited, but its is preferred
For 1 to 40.According to an embodiment, alkyl has 1 to 20 carbon atom.According to another embodiment, alkyl have 1 to
10 carbon atoms.According to further embodiment, alkyl has 1 to 6 carbon atom.The instantiation of alkyl includes methyl, second
Base, propyl group, n-propyl, isopropyl, butyl, normal-butyl, isobutyl group, the tert-butyl group, sec-butyl, 1- methyl-butvls, 1- ethyls-fourth
Base, amyl group, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1- methyl amyls, 2- methyl amyls, 4- methyl-
2- amyl groups, 3,3- dimethylbutyls, 2- ethyl-butyls, heptyl, n-heptyl, 1- methylhexyls, cyclopentyl-methyl, cyclohexyl first
Base, octyl group, n-octyl, t-octyl, 1- methylheptyls, 2- ethylhexyls, 2- propylpentyls, n-nonyl, 2,2- dimethyl heptyl,
1- Ethyl-propyls, 1,1- Dimethyl-propyls, isohesyl, 2- methyl amyls, 4- methylhexyls, 5- methylhexyls etc., but it is unlimited
In this.
In the present specification, aryl is not particularly limited, but preferably has 6 to 60 carbon atoms, and can be monocyclic
Aryl or polyaromatic.According to an embodiment, aryl has 6 to 30 carbon atoms.According to another embodiment, aryl
With 6 to 20 carbon atoms.As monocyclic aryl, aryl can be phenyl, xenyl, terphenyl etc., but not limited to this.It is more
The example of cyclophane base include naphthyl, anthryl, phenanthryl, pyrenyl,Base,Base (crycenyl group), fluorenyl etc., but it is unlimited
In this.
An embodiment according to the present invention, there is provided the method for manufacturing insulating layer, it comprises the following steps：Will
The opposed surface that the metal layer of carrier film is stained with one surface is adhered to comprising alkali soluble resins and thermal curable bonding
In the polymer resins layers of agent；Patterned photosensitive resin layer is formed in the carrier film；Remove by the patterned light
The carrier film of quick resin bed exposure and the metal layer are to form patterned metal layer；From the patterned metal layer
It is upper to separate and remove the carrier film；Make by the polymer resins layers alkali development of the patterned metal layer exposure；With
And make the polymer resins layers heat cure after the alkali development.
The method for manufacturing insulating layer according to an embodiment, the inventors discovered that, in alkali-soluble polymer tree
The figuratum metal layer of tool introduced in lipid layer serves as the mask for making polymer resins layers alkali development, sudden and violent by metal layer pattern
The fluoropolymer resin layer segment of dew is removed by alkaline development, and the fluoropolymer resin layer segment quilt not exposed by metal layer pattern
Alkaline developer is protected from, therefore, fine pattern can be formed in polymer resins layers chemically.
Fine figure it has also been found that, compared with the insulating layer by laser machining manufacture, is formed by the above method by experiment
The insulating layer of case can be rapidly formed with low cost, and manufactured final insulating layer can realize that excellent physics is special
Property.Based on the discovery that develop the present invention.
In addition, compared with using the situation of conventional photosensitive insulating material manufacture insulating layer, due to the insulation finally manufactured
Layer is included as the cured product of the thermal curable resin of non-photosensitivity insulating materials, so greatly reducing photoinitiator or polymerization inhibitor
Content or can not use them.This allows to insulating layer of the manufacture with excellent mechanical property, for example, can
Interfacial separation characteristic between the insulating layer and conductive layer that are produced by photoinitiator or polymerization inhibitor reduces.
Especially, the embodiment be used for manufacture the method for insulating layer, when introducing gold in the polymer resins layers
When belonging to layer as mask, since the process is carried out in the case where carrier film adheres to metal layer, so not only the metal layer can
With easily laminated by carrier film, and the carrier film can be removed at the same time by the etchant identical with metal layer.Therefore,
Metal layer can also be easily etched in the state of carrier film is stained with.
In addition, in order to form pattern in carrier film and metal layer, the physics between carrier film and metal layer can be passed through
Peel off and easily remove the photosensitive resin layer introduced on a carrier film.Therefore, even without single stripper processing with except
Photosensitive resin layer is removed, is also advantageous in terms of process efficiency.
In addition, because the alkali soluble resins used in the method for being used to manufacture insulating layer of an embodiment is in molecule knot
At the same time comprising the characteristic cyclic imide functional group through amino substitution and acidic functionality in structure, it is possible to pass through acid official
It can roll into a ball to realize alkali solubility, and can be sub- by the typical annular acyl substituted through amino when being reacted with thermal curable binding agent
Amine functional group improves cured density, so as to improve resistance to thermal reliability and mechanical property, and also improves in another interface
Adhesiveness.
Thus, the polymer resins layers comprising alkali soluble resins can have the boundary improved with the metal layer for being laminated in upside
Face adhesiveness, and specifically, can have than metal layer and the interfacial adhesion being laminated between the carrier film on metal layer top
The bonding force of property bigger.Therefore, as described later, it is possible that the physics between carrier film and metal layer, which is peeled off,.
Specifically, may comprise steps of for manufacturing the method for insulating layer：Carrier will be stained with one surface
The opposed surface of the metal layer of film is adhered in the polymer resins layers comprising alkali soluble resins and thermal curable binding agent；Carrying
Patterned photosensitive resin layer is formed on body film；The carrier film exposed by patterned photosensitive resin layer and metal layer are removed with shape
Into patterned metal layer；Separated from patterned metal layer and remove carrier film；Make what is exposed by patterned metal layer
Polymer resins layers alkali development；And make polymer resins layers heat cure after alkali development.
The details of each step is described below.
The opposed surface for the metal layer that carrier film is stained with one surface is adhered to comprising alkali soluble resins and can
Step in the polymer resins layers of hot setting adhesive
Adhering to the opposed surface that the metal layer of carrier film is stained with one surface comprising alkali soluble resins and
In step in the polymer resins layers of thermal curable binding agent, polymer resins layers mean to include alkali soluble resins by drying
The film formed with the polymer resin composition of thermal curable binding agent.
Polymer resins layers can with individualism, or can be formed in include semi-conducting material base material (such as electricity
Road plate, piece, multilayer printed circuit board etc.) on state exist.The example that the method for polymer resins layers is formed on base material does not have
There is special limitation, but it is, for example, possible to use polymer resin composition is wherein applied directly to the method on base material, Huo Zheqi
It is middle to be stained with coated in carrier film or thereon polymer resin composition on the metal layer of carrier film then laminated with base material
Method etc..
In addition, the opposed surface for the metal layer that carrier film is stained with one surface is adhered to comprising alkali soluble resins
It can include such method with the example of the method in the polymer resins layers of thermal curable binding agent：Alkali solubility tree will be included
The polymer resin composition of fat and thermal curable binding agent is coated to metal layer that carrier film is stained with one surface
In opposed surface, and the dry coating.
Polymer resins layers can include alkali soluble resins and thermal curable binding agent.
Based on the alkali soluble resins of 100 parts by weight, polymer resins layers can include 1 parts by weight to 150 parts by weight, 10 weights
Part is measured to 100 parts by weight or 20 parts by weight to the thermal curable binding agent of the amount of 50 parts by weight.When containing for thermal curable binding agent
Amount it is too high when, polymer resins layers can developability deterioration and intensity may be decreased.On the contrary, containing when thermal curable binding agent
When measuring too low, not only polymer resins layers is excessively developed, but also coat uniformity and may be decreased.
Thermal curable binding agent can include epoxy group；And selected from thermal curable functional group, oxetanyl, ring-type
Ether, cyclic thioether base, cyanide-based, dimaleoyl imino and benzoAt least one of piperazine base functional group.That is, can heat
Epoxy group must be included by curing binding agent, and in addition to epoxy group, can also include oxetanyl, cyclic ether group, ring
Shape thioether group, cyanide-based, dimaleoyl imino, benzoThe mixture of piperazine base or both or more person.It is such
Thermal curable binding agent can by heat cure and alkali soluble resins etc. formed cross-bond, so that it is guaranteed that the heat resistance of insulating layer or
Mechanical property.
More specifically, as thermal curable binding agent, it can use in molecule and contain both or more in above-mentioned functional group
The multifunctional resin compound of person.
Multifunctional resin compound can include containing two or more cyclic ether groups and/or cyclic thioether base in molecule
The resin of (being hereinafter referred to as ring-type (sulphur) ether).
The thermal curable binding agent containing two or more ring-type (sulphur) ethers can be to have choosing in molecule in molecule
From any of 3 yuan, 4 yuan or 5 yuan cyclic ether groups or cyclic thioether base or the compound of two kinds of two or more.
The example of the compound with two or more cyclic thioether bases is included by JapanEpoxy Resins in molecule
Co., bisphenol A-type episulfide resin YL 7000 of Ltd. manufactures etc..
In addition, multifunctional resin compound can be included in molecule containing the multifunctional of at least two or more a epoxy groups
In epoxide, molecule the multifunctional oxetane compound containing at least two or more oxetanyls or
Person is contained in the episulfide resin of at least two or more thioether groups, molecule containing at least two or more cyanide-baseds
Multifunctional cyanate ester compound or molecule in contain at least two or more benzosThe multifunctional benzo of piperazine base
Piperazine compound etc..
The instantiation of multi-functional epoxy compound can include bisphenol A type epoxy resin, hydrogenated bisphenol A type asphalt mixtures modified by epoxy resin
Fat, brominated bisphenol a type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenolic resin varnish type epoxy resin, benzene
Phenol phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, N- glycidyl epoxies, the phenolic aldehyde of bisphenol-A
Novolac epoxy resins, union II cresols epoxy resin, xenol epoxy resin, chelating epoxy resin, glyoxal epoxy resin, contain
The epoxy resin of amino, rubber-modified epoxy resin, bicyclopentadiene phenol epoxy resin, phthalic acid 2-glycidyl
Ester resin, heterocyclic epoxy resin, four glycidyl group dimethylbenzene phenolic group ethane resin, through organic-silicon-modified epoxy resin, warp
Epoxy resin that 6-caprolactone is modified etc..In addition, in order to assign anti-flammability, can use to have wherein to introduce has phosphorus etc.
The compound of the structure of atom.These epoxy resin can improve adhesiveness, the welding of such as solidified coating film by heat cure
The characteristic of heat resistance, resistance to electroless plating etc..
The example of multifunctional oxetane compound can include multifunctional oxetanes, such as double [(3- methyl-
3- oxetanylmethoxies) methyl] ether, double [(3- ethyl -3- oxetanylmethoxies) methyl] ethers, 1,4- be double
Double [(3- ethyl -3- oxetanylmethoxies) first of [(3- methyl -3- oxetanylmethoxies) methyl] benzene, 1,4-
Base] benzene, acrylic acid (3- methyl -3- oxetanyls) methyl esters, acrylic acid (3- ethyl -3- oxetanyls) methyl esters, first
Base acrylic acid (3- methyl -3- oxetanyls) methyl esters, methacrylic acid (3- ethyl -3- oxetanyls) methyl esters and
Its oligomer or copolymer, and in addition can also include the etherification product of oxetanes alcohol and hydroxy-containing resin, institute
State hydroxy-containing resin such as novolac resin, poly- (4-Vinyl phenol), cardo types bis-phenol, calixarenes, cup resorcinol cup
Aromatic hydrocarbons (calixresorcinarene), silsesquioxane etc..It is furthermore it is possible to single including the unsaturation with oxetanes ring
The copolymer of body and (methyl) alkyl acrylate.
The example of multifunctional cyanate ester compound can include bisphenol A cyanate ester resin, bisphenol E-type cyanate resin,
Bisphenol-f type cyanate ester resin, bisphenol S type cyanate ester resin, bis-phenol M types cyanate ester resin, phenolic varnish type cyanate ester resin, benzene
Phenol phenolic varnish type cyanate ester resin, cresol novolak type cyanate ester resin, bisphenol-A phenolic varnish type cyanate ester resin,
Biphenyl phenolic cyanate ester resin, its oligomer or copolymer etc..
The example of multifunctional maleimide compound can include 4,4'- diphenyl methane dimaleimides, phenylmethane
Bismaleimide, a phenylmethane bismaleimide, bisphenol-A diphenyl ether bismaleimide, 3,3'- dimethyl -5,5'-
Diethyl -4,4'- diphenyl methane dimaleimides, 4- methyl isophthalic acids, 3- phenylenes bismaleimide, 1,6'- spans carry out acyl
Imines-(2,2,4- trimethyls) hexane etc..
Multifunctional benzoThe example of piperazine compound can include bisphenol A-type benzoPiperazine resin, bisphenol-f type benzo
Piperazine resin, phenolphthalein type benzoPiperazine resin, phenyl disulfide phenolic benzoPiperazine resin, dicyclopentadiene-type benzoPiperazine resin,
Double (3,4- dihydro -2H-1,3- the benzos of 3,3- (methylene -1,4- diphenylenes)Piperazine) resin etc..
The more specific examples of multifunctional resin compound can include YDCN-500-80P (KukdoChemical
Co.Ltd.), phenol novolak type cyanide ester resin PT-30S (Lonza Ltd.), phenylmethane type maleimide resin
BMI-2300 (Daiwa Kasei Co., Ltd.), Pd type benzosPiperazine resin (Shikoku Chemicals) etc..
Meanwhile alkali soluble resins can be included in the cyclic imide functional group selected from acidic functionality and through amino substitution
At least one or more person or both or more person.The example of acidic functionality can include but is not limited to carboxyl or phenol
Base.Alkali soluble resins includes at least one or more or two or more acidic functionalities so that polymer resins layers
The alkali development characteristic of higher is shown, and the developing rate of polymer resins layers can be controlled.
The cyclic imide functional group substituted through amino includes amino and cyclic imide base in the structure of functional group, and
And can include it is therein at least one or more person or both or more person.Because alkali soluble resins include it is at least one or
Cyclic imide functional groups that more or two or more substitute through amino, wherein exist so alkali soluble resins has
The structure of a large amount of reactive hydrogens contained in amino.Therefore, it is reactive with thermal curable binding agent during heat cure is improved
Meanwhile cured density can be increased, so as to improve resistance to thermal reliability and mechanical property.
Further, since there are substantial amounts of cyclic imide functional group in alkali soluble resins, polarity is due to cyclic imide
The carbonyl and the tertiary amine groups that are included in functional group and increase so that the interfacial adhesion of alkali soluble resins can increase.Thus, comprising
The polymer resins layers of alkali soluble resins can have increased interfacial adhesion with the metal layer for being laminated in upside, and specifically
Ground, can have the bonding force than the interfacial adhesion bigger between metal layer and the carrier film being laminated on metal layer top.
Therefore, as described later, it is possible that the physics between carrier film and metal layer, which is peeled off,.
More specifically, the cyclic imide functional group through amino substitution can include the function represented by formula 1 below
Group.
[chemical formula 1]
In chemical formula 1, R1For the alkylidene with 1 to 10 carbon atom, 1 to 5 carbon atom or 1 to 3 carbon atom
Or alkenyl, and " * " mean bonding point.Alkylidene is the divalent functional groups derived from alkane, for example, linearly, branched or cyclic group
Group, and including methylene, ethylidene, propylidene, isobutylidene, sub- sec-butyl, the sub- tert-butyl group, pentylidene, hexylidene etc..It is sub-
One or more hydrogen atoms included in alkyl can be substituted by other substituent, and the example bag of other substituent
Include the alkyl with 1 to 10 carbon atom, the alkenyl with 2 to 10 carbon atoms, the alkynyl with 2 to 10 carbon atoms, tool
Have the aryl of 6 to 12 carbon atoms, the heteroaryl with 2 to 12 carbon atoms, the aryl alkyl with 6 to 12 carbon atoms,
Halogen atom, cyano group, amino, amidino groups, nitro, amide groups, carbonyl, hydroxyl, sulfonyl, carbamate groups, have 1 to 10
Alkoxy of carbon atom etc..
Term " substitution " as used herein means to be bonded another functional group in compound with instead of hydrogen atom, and substitutes
Position does not limit, as long as it is the position (that is, the commutable position of substituent) for substituting hydrogen atom.When two or more
During a substituent substitution, two or more substituents can be same to each other or different to each other.
Alkenyl means above-mentioned alkylidene therebetween or at least one carbon-to-carbon double bond is contained in end, the example include ethene,
Propylene, butylene, hexene, acetylene etc..One or more hydrogen atoms in alkenyl can in a manner of identical with alkylidene quilt
Substituent substitutes.
Preferably, the cyclic imide functional group through amino substitution can be the functional group represented by formula 2 below.
[chemical formula 2]
In chemical formula 2, " * " means bonding point.
As described above, alkali soluble resins includes cyclic imide functional group and acidic functionality through amino substitution.Specifically
Ground, acidic functionality can be bonded at least one end of the cyclic imide functional group through amino substitution.At this time, through amino
Substituted cyclic imide functional group and acidic functionality by the alkylidene that is substituted or is unsubstituted or can be substituted
Or the arlydene that is unsubstituted and be bonded.For example, acidic functionality can by the alkylidene that is substituted or is unsubstituted or
The arlydene for being substituted or being unsubstituted is bonded to the end of the amino included in the imide functionality through amino substitution.It is acid
Functional group can be bonded to through ammonia by the alkylidene for being substituted or being unsubstituted or the arlydene for being substituted or being unsubstituted
The end of the cyclic imide functional group included in the imide functionality of base substitution.
More specifically, the end of the amino included in the cyclic imide functional group through amino substitution means in chemical formula 1
Amino in the nitrogen-atoms that includes, and the end of the imide functionality included in the cyclic imide functional group through amino substitution
End means the nitrogen-atoms included in the cyclic imide functional group in chemical formula 1.
Alkylidene is the divalent functional groups derived from alkane, for example, linearly, branched or cyclic group, and including methylene
Base, ethylidene, propylidene, isobutylidene, sub- sec-butyl, the sub- tert-butyl group, pentylidene, hexylidene etc..One included in alkylidene
A or more hydrogen atom can be substituted by other substituent, and the example of other substituent includes having 1 to 10
The alkyl of carbon atom, the alkenyl with 2 to 10 carbon atoms, the alkynyl with 2 to 10 carbon atoms, with 6 to 12 carbon originals
Son aryl, the heteroaryl with 2 to 12 carbon atoms, the aryl alkyl with 6 to 12 carbon atoms, halogen atom, cyano group,
Amino, amidino groups, nitro, amide groups, carbonyl, hydroxyl, sulfonyl, carbamate groups, the alkoxy with 1 to 10 carbon atom
Deng.
Arlydene means the divalent functional groups derived from aromatic hydrocarbons, such as cyclic group, and can include phenyl, naphthyl
Deng.One or more hydrogen atoms included in arlydene can be substituted by other substituent.The example of substituent includes tool
Have the alkyl of 1 to 10 carbon atom, the alkenyl with 2 to 10 carbon atoms, the alkynyl with 2 to 10 carbon atoms, with 6 to
The aryl of 12 carbon atoms, the heteroaryl with 2 to 12 carbon atoms, the aryl alkyl with 6 to 12 carbon atoms, halogen are former
Son, cyano group, amino, amidino groups, nitro, amide groups, carbonyl, hydroxyl, sulfonyl, carbamate groups, have 1 to 10 carbon atom
Alkoxy etc..
The example of method for producing alkali soluble resins is not particularly limited, but for example, alkali soluble resins can pass through
The reactions of ring-type unsaturated acyl group with imine moiety and amine compounds produces.In this case, ring-type unsaturated acyl imidization
At least one of compound and amine compounds may be embodied in the acidic functionality of its end substitution.That is, acidic functionality can be with
Substitute in the end of both ring-type unsaturated acyl group with imine moiety, amine compounds or these compounds.The details of acidic functionality
As described above.
Cyclic imide compound is the compound for including above-mentioned cyclic imide functional group, and ring-type unsaturated acyl is sub-
Amine compounds mean to include the compound of at least one unsaturated bond (that is, double or triple bonds) in cyclic imide compound.
Alkali soluble resins can be by including in the amino and ring-type unsaturated acyl group with imine moiety that are included in amine compounds
The reactions of double or triple bonds produce.
The example for the weight ratio that ring-type unsaturated acyl group with imine moiety is reacted with amine compounds is not particularly limited, but example
Such as, the ring-type unsaturated acyl group with imine moiety based on 100 parts by weight, amine compounds can be by with 10 parts by weight to 80 parts by weight
Or 30 the amounts of parts by weight to 60 parts by weight mix and react.
The example of ring-type unsaturated acyl group with imine moiety includes the maleimide compound of N substitutions.Term " N- substitutions "
Mean the nitrogen-atoms that functional group replaces bonded hydrogen atoms to be included into maleimide compound, and the Malaysia substituted according to N-
The number of imide compound, the maleimide compound of N- substitutions can be categorized as the maleimide of the N- substitutions of simple function
Amine compounds and the maleimide compound of polyfunctional N- substitutions.
The maleimide compound of the N- substitutions of simple function is the nitrogen included in one of maleimide compound
The compound that atom is substituted by functional group, the maleimide compound of polyfunctional N- substitutions is two of which or more horse
The compound that the nitrogen-atoms for coming in each in imide compound to include is bonded by functional group.
In the maleimide compound that the N- of simple function substitutes, the nitrogen-atoms that is included in maleimide compound
Upper substituted functional group can include but is not limited to various known aliphatic, alicyclic or aromatic functional groups, and in nitrogen
The functional group substituted on atom can include the official that wherein aliphatic, alicyclic or aromatic functional groups are substituted by acidic functionality
Can group.The details of acidic functionality is as described above.
The instantiation of the maleimide compound of the N- substitutions of simple function includes o-tolyl maleimide, to hydroxyl
Phenyl maleimide, to carboxy phenyl maleimide, dodecyl maleimide etc..
In the maleimide compound of polyfunctional N- substitutions, between two or more maleimide compounds
In it is each in functional group between nitrogen-nitrogen key for including can include but is not limited to various known aliphatic, it is alicyclic or
Aromatic functional groups.In instantiation, 4,4'- diphenyl-methanes functional group etc. can be used.The function substituted on nitrogen-atoms
Group can include the functional group that wherein aliphatic, alicyclic or aromatic functional groups are substituted by acidic functionality.Acidic functionality
Details it is as described above.
The instantiation of the maleimide compound of polyfunctional N- substitutions includes 4,4'- diphenyl-methane bismaleimides
Amine (BMI-1000, BMI-1100 etc., are available from Daiwakasei Industry Co., Ltd.s), phenylmethane bismaleimide
Amine, metaphenylene methane bismaleimide, bisphenol-A diphenyl ether bismaleimide, 3,3'- dimethyl -5,5'- diethyls
Base -4,4'- diphenyl methane dimaleimides, 4- methyl isophthalic acids, 3- phenylenes bismaleimide, 1,6'- bismaleimide -
(2,2,4- trimethyls) hexane etc..
Amine compounds can include at least one amino (- NH in the molecular structure2) primary amino-compound.More preferably
Ground, can use the carboxylic acid compound through amino substitution, the multi-functional amine compounds comprising at least two amidos or its mixing
Thing.
In the carboxylic acid compound substituted through amino, carboxylic acid compound is to include carboxylic acid (- COOH) functional group in the molecule
Compound, and according to the species for the hydrocarbon being bonded with carboxylic acid functional, it can include all aliphatic, alicyclic and fragrant
Fragrant race's carboxylic acid.Because by the carboxylic acid compound substituted through amino, a large amount of carboxylics of acidic functionality are included as in alkali soluble resins
Acid functional group, thus alkali soluble resins can developability can improve.
Term " substitution " means to be bonded another functional group in compound with instead of hydrogen atom, and the ammonia in carboxylic acid compound
The position of base substitution does not limit, as long as it is the position for substituting hydrogen atom.Number of amino groups to be replaced can be 1 or more
It is more.
The instantiation of carboxylic acid compound through amino substitution includes 20 kinds of a-amino acids, 4-Aminobutanoicacid, 5- amino penta
Acid, 6-aminocaprolc acid, 7- aminoheptylic acids, 8- aminocaprylic acids, 4-aminobenzoic acid, 4- aminophenyl acetic acids, 4- aminocyclohexane carboxylics
Acid etc., these are known to be the raw material of protein.
In addition, the multi-functional amine compounds comprising two or more amino can be to include at least two amino in molecule
(-NH2) compound, and according to the species of the hydrocarbon with amino bonded, it can include all aliphatic, alicyclic and fragrant
The polyfunctional amine of fragrant race.By including the multi-functional amine compounds of at least two amino, can improve alkali soluble resins flexibility,
Toughness, to adhesiveness of copper foil etc..
The instantiation of multi-functional amine compounds comprising two or more amino includes 1,3- cyclohexane diamines, 1,4-
Cyclohexane diamine, 1,3- double (amino methyl)-hexamethylenes, Isosorbide-5-Nitrae-bis- (amino methyl)-hexamethylene, double (amino methyls)-drop ice
Piece alkene, octahydro -4,7- methylenes bridged indene -1 (2), 5 (6)-dimethylamine (5 (6)-dimethanamine), 4,4' methylene bis (ring
Hexylamine), 4,4' methylene bis (2- methyl cyclohexylamines), isophorone diamine, 1,3- phenylenediamines, 1,4- phenylenediamines, 2,5- diformazans
Base -1,4- phenylenediamines, 2,3,5,6- tetramethyl -1,4- phenylenediamines, the fluoro- 1,3- phenylenediamines of 2,4,5,6- tetra-, 2,3,5,6- tetra- are fluoro-
Isosorbide-5-Nitrae-phenylenediamine, 4,6-diaminoresorcinol, 2,5- diaminostilbenes, 4- dimercaptobenzenes, 3- amino-benzylamines, 4- amino-benzylamines,
M-xylene diamine, paraxylene diamines, 1,5- diaminonaphthalenes, 2,7 diamin of luorene, 2,6- diamino-anthraquinones, a ditolyl
Amine, o-tolidine, 3,3', 5,5'- tetramethyl benzidines (TMB), dianisidine, 4,4' methylene bis (2- chloroanilines),
3,3'-diaminobenzidine, 2,2'- double (trifluoromethyl)-benzidine, 4,4'- diaminourea octafluorobiphenyl, 4,4'- diaminourea-right
Terphenyl, 3,3'- diaminodiphenylmethane, 3,4'- diaminodiphenylmethane, 4,4'- diaminodiphenylmethane, 4,4'- diaminos
Base -3,3'- dimethyl diphenyl methanes, 4,4' methylene bis (2- ethyl -6- methylanilines), 4,4' methylene bis (2,6- bis-
Ethyl aniline), 3,3'- diaminobenzophenones, 4,4'- diaminobenzophenones, 4,4'- ethylenes aniline, 4,4'- diaminos
Double (3- amino-4-hydroxylphenyls) propane of base -2,2'- dimethyl bibenzyl, 2,2'-, double (3- the aminophenyls)-hexafluoros third of 2,2'-
Double (3- the aminophenyls)-hexafluoropropane of alkane, 2,2'-, double (3- amino -4- the aminomethyl phenyls)-hexafluoropropane of 2,2'-, 2,2'- are double
Double [2- (the 4- of (3- amino-4-hydroxylphenyls)-hexafluoropropane, α, α '-bis- (4- aminophenyls) -1,4- diisopropyl benzenes, 1,3-
Aminophenyl) -2- propyl group] benzene, double (4- the aminophenyls)-hexamethylenes of 1,1'-, double (4- the aminophenyls)-fluorenes of 9,9'-, 9,9'- be double
Double (4- amino -3- aminomethyl phenyls) fluorenes of (4- amino -3- chlorphenyls) fluorenes, 9,9'- pairs of (4- amino -3- fluorophenyls) fluorenes, 9,9'-,
Double (3- the amino-benzene oxygens)-benzene of 3,4'- diaminodiphenyl ethers, 4,4'- diaminodiphenyl ethers, 1,3-, double (the 4- aminobenzene oxygen of 1,3-
Base)-benzene, double (4- the amino-benzene oxygens)-benzene of 1,4-, double (4- amino -2- the 4-trifluoromethylphenopendants)-benzene of 1,4-, the double (4- of 4,4'-
Amino-benzene oxygen)-biphenyl, double [4- (the 4- amino-benzene oxygens)-phenyl] propane of 2,2'-, 2,2'- it is double [4- (4- amino-benzene oxygens)-
Phenyl] hexafluoropropane, double (2- aminophenyls) thioethers, double (4- aminophenyls) thioethers, double (3- aminophenyls) sulfones, double (4- ammonia
Base phenyl) sulfone, double (3- amino-4-hydroxies) sulfones, double [4- (3- amino-benzene oxygens)-phenyl] sulfones, double [4- (4- aminobenzene oxygen
Base)-phenyl] sulfone, o-tolidine sulfone, 3,6- diaminocarbazoles, 1,3,5- tri- (4- aminophenyls)-benzene, double (the 3- amino of 1,3-
Propyl group)-tetramethyl disiloxane, 4,4'- diaminobenzenes formailide, 2- (3- aminophenyls) -5- aminobenzimidazoles, 2-
(4- aminophenyls) -5- amino benzosAzoles, 1- (4- aminophenyls) -2,3- dihydro -1,3,3- trimethyl -1H- indenes -5- amine,
4,6- diamino resorcins, 2,3,5,6- pyridines tetramine, include the multifunctional of Shin-Etsu Silicone siloxane structures
Amine (PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, X-22-9409),
Polyfunctional amine (Dow Corning 3055), the polyfunctional amine comprising polyether structure comprising Dow Corning siloxane structures
(Huntsman, BASF) etc..
In addition, alkali soluble resins can include at least one repetitive unit represented by formula 3 below and at least one
The repetitive unit represented by formula 4 below.
[chemical formula 3]
In chemical formula 3, R2Alkylidene for direct key, with 1 to 20 carbon atom, with 1 to 20 carbon atom
Alkenyl or the arlydene with 6 to 20 carbon atoms, and " * " mean bonding point.
[chemical formula 4]
In chemical formula 4, R3Alkylidene for direct key, with 1 to 20 carbon atom, with 1 to 20 carbon atom
Alkenyl or the arlydene with 6 to 20 carbon atoms, R4For-H ,-OH ,-NR5R6, halogen or the alkane with 1 to 20 carbon atom
Base, R5And R6Hydrogen, the alkyl with 1 to 20 carbon atom or the aryl with 6 to 20 carbon atoms can be each independently,
And " * " means bonding point.
Preferably, in formula 3, R2For phenylene, in formula 4, R3For phenylene and R4Can be-OH.
Meanwhile in addition to the repetitive unit represented by chemical formula 3 and the repetitive unit represented by chemical formula 4, alkali solubility tree
Fat can also include the repetitive unit based on vinyl.Repetitive unit based on vinyl is comprising at least one or more in molecule
The repetitive unit included in the homopolymer of the monomer based on vinyl of multiple vinyl, and the reality of the monomer based on vinyl
Example can include but is not limited to ethene, propylene, isobutene, butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride,
Maleimide etc..
At least one represented comprising at least one repetitive unit represented by above-mentioned chemical formula 3 and by above-mentioned chemical formula 4
The alkali soluble resins of repetitive unit can by make comprising by formula 5 below represent repetitive unit polymer, by following
The amine and reacted by the amine of formula 7 below expression to produce that chemical formula 6 represents.
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
In chemical formula 5 to 7, R2To R4It is identical described in chemical formula 3 and 4 with more than, and " * " mean bonding point.
The instantiation of polymer comprising the repetitive unit represented by chemical formula 5 can include but is not limited to SMA (Cray
Valley), Xiran (Polyscope), Scripset (Solenis), Isobam (Kuraray), Polyanhydride Resin (Chevron
Phillips Chemical Company), Maldene (Lindau Chemicals) etc..
In addition, comprising at least one repetitive unit represented by above-mentioned chemical formula 3 and at least one by above-mentioned 4 table of chemical formula
The alkali soluble resins of the repetitive unit shown can be by making by the compound of formula 8 below expression and by formula 9 below table
The compound shown is reacted to produce.
[chemical formula 8]
[chemical formula 9]
In chemical formula 8 and 9, R2To R4It is identical described in chemical formula 3 and 4 with more than.
In addition, alkali soluble resins can be known conventional to contain carboxy resin comprising carboxyl or phenolic group in the molecule thereof
Or containing phenol resin.Preferably, the mixture containing carboxy resin or containing carboxy resin and containing phenol resin can be used.
Example containing carboxy resin includes the resin that following (1) is listed into (7), but not limited to this.
(1) it is then anti-with multi-anhydride by making polyfunctional epoxy resin be reacted with saturation or undersaturated monocarboxylic acid
Should and obtain contain carboxy resin,
(2) by reacting bifunctional epoxy resin and difunctionality phenol and/or dicarboxylic acids, then react with multi-anhydride and
What is obtained contains carboxy resin,
(3) by making multifunctional phenol resin with having the compound of 1 epoxy group to react in the molecule, then and polyacid
Anhydride reactant and obtain contain carboxy resin,
(4) by making the compound with two or more alcoholic extract hydroxyl groups in the molecule and multi-anhydride react and acquisition
Containing carboxy resin,
(5) by the copolymerization of the polyamic acid resin or polyamic acid resin that obtain diamines and dianhydride resin reaction
Thing,
(6) copolymer of polyacrylic resin or polyacrylic resin obtained by being reacted with acrylic acid,
(7) reacted by the acid anhydrides of maleic anhydride and copolymer-maleic anhydride and weak acid, diamines, imidazoles or dimethyl sulfoxide (DMSO)
The resin for making maleic anhydride resin open loop and preparing.
More specific examples containing carboxy resin include CCR-1291H (Nippon Kayaku), SHA-1216CA60 (Shin-
A T＆C), the mixture of Noverite K-700 (Lubrizol) or both or more persons.
Example containing phenol resin is not particularly limited, but for example, novolac resin can be used alone or in combination,
Such as phenol resol resins, cresol novolac resin, Bisphenol F (BPF) novolac resin；Or based on bisphenol-A
Resin, such as 4,4'- (1- (4- (2- (4- hydroxy phenyls) propyl- 2- yls) phenyl) ethane -1,1- diyl) diphenol.
Polymer resins layers can also be included selected from thermal curing catalyst, inorganic filler, levelling agent, dispersant, releasing agent
With at least one of metal adhesion promoters additive.
As measured by KOH titration, the acid number of alkali soluble resins can be 50mgKOH/g to 250mgKOH/g or
70mgKOH/g to 200mgKOH/g.The example of method for measuring the acid number of alkali soluble resins is not particularly limited, but for example can be with
Use following methods.Prepare the KOH solution (solvent that concentration is 0.1N：Methanol) aqueous slkali is used as, prepare α-naphtholbenzine methanol
(pH：0.8 to 8.2 yellow, 10.0 blue-greens) it is used as indicator.Then, collect about 1g to 2g alkali soluble resins as sample simultaneously
Dissolving in 50g dimethylformamides (DMF) solvent added with indicator, is then titrated with alkali soluble agent wherein.Acid number is used in
The amount of used alkali soluble agent is determined in units of mg KOH/g when being properly done.
When the acid number of alkali soluble resins excessively decreases below 50mgKOH/g, the developing property of alkali soluble resins reduces,
So that it is difficult to developing process.In addition, when the acid number of alkali soluble resins excessively increases to greater than 250mgKOH/g,
It may occur and the phase separation of other resins since polarity increases.
Thermal curing catalyst is used for the heat cure for promoting thermal curable binding agent.The example of thermal curing catalyst includes imidazoles
Derivative, such as imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole, 2- phenylimidazoles, 4- phenyl miaows
Azoles, 1- cyano ethyl -2- phenylimidazoles and 1- (2- cyano ethyls) -2-ethyl-4-methylimidazole；Amine compounds, such as double cyanogen
Amine, benzyl dimethylamine, 4- (dimethylamino)-N, N- dimethyl benzylamine, 4- methoxyl groups-N, N- dimethyl benzylamine and 4- methyl-
N, N- dimethyl benzylamine；Hydrazine compound, such as adipic dihydrazide and sebacic dihydrazide；Phosphorus compound, such as triphenylphosphine；
Etc..The example of commercial product include by Shikoku Chemicals Corporation manufacture 2MZ-A, 2MZ-OK,
2PHZ, 2P4BHZ and 2P4MHZ (ProductName of imidazolium compounds)；The U-CAT3503N that is manufactured by San-Apro Ltd. and
UCAT3502T (ProductName of the block isocyanate compound of dimethylamine), and DBU, DBN, U-CATS A102, U-
CAT5002 (bicyclic amidine compound and its salt).However, thermal curing catalyst is not limited to these, or for epoxy resin
Or the thermal curing catalyst of oxetane compound, or accelerate epoxy group and/or oxetanyl and carboxyl reaction
Compound.These catalyst can be used alone or be used as the mixture of two or more.In addition it is possible to use S-
Pyrrolotriazine derivatives, such as guanamines, acetylguanamine, benzoguanamine, melamine, 2,4- diaminourea -6- methacryloxy second
Base-S- triazines, 2- vinyl -4,6- diaminourea-S- triazines, 2- vinyl -4,6- diaminourea-S- triazines, 2- vinyl -4,6-
Diaminourea-S- triazines-isocyanuric acid adduct, 2,4- diaminourea -6- methacryloxyethyls-S- triazines-isocyanuric acid
Addition product etc..Preferably, also playing the compound of these adhesiveness imparting agents can be applied in combination with thermal curing catalyst.
The example of inorganic filler includes silica, barium sulfate, barium titanate, talcum, clay, magnesium carbonate, calcium carbonate, oxidation
The mixture of aluminium, aluminium hydroxide, mica or both or more person.
The content of inorganic filler is not particularly limited.However, in order to realize the high rigidity of polymer resins layers, based on 100
The all resins component included in the polymer resins layers of parts by weight, can be with 100 parts by weight or more, 100 parts by weight to 600
The amount addition inorganic filler of parts by weight, 150 parts by weight to 500 parts by weight or 200 parts by weight to 500 parts by weight.
The example of releasing agent includes polyolefin-wax, such as low-molecular-weight polypropylene and low molecular weight polyethylene, ester type waxes, Brazil
Palm wax, paraffin etc..
Metal adhesion promoters can be the material for not making metal material produce surface deterioration or clarity issues, for example,
Silane coupling agent, organic metal coupling agent etc..
Levelling agent be used for film coat during remove surface on protrusion or depression, it is, for example, possible to use be available from
BYK-380N, BYK-307, BYK-378 and BYK-350 of BYK-Chemie GmbH etc..
In addition, polymer resins layers can also include can cause the molecular weight of phase separation for 5000 or bigger resin or
Elastomer.Thus, it is possible to the cured product of polymer resins layers is set to be subjected to roughening processing.It is 5000 or bigger to measure molecular weight
Resin or the example of method of molecular weight of elastomer be not particularly limited, for example, it means by GPC (gel infiltration colors
Spectrometry) according to the weight average molecular weight of polystyrene measurement.The process of weight average molecular weight is being measured according to polystyrene by GPC
In, commonly known analytical equipment, detector such as differential refractive index detector and analytical column can be used.It can use usual
The condition of the temperature of application, solvent and flow.The instantiation of measuring condition include 30 DEG C temperature, tetrahydrofuran (THF) and
The flow of 1mL/min.
In addition, in order to assign photocurable characteristic to polymer resins layers, polymer resins layers can also contain light
The thermal curable binding agent of reactive unsaturated group or the alkali solubility containing photoreactivity unsaturated group and photoinitiator
Resin.Thermal curable binding agent containing photoreactivity unsaturated group contains photoreactivity unsaturated group and light-initiated
The instantiation of the alkali soluble resins of agent is not particularly limited, and can without limitation use and be combined with light-curable resin
The various compounds used in the relevant technical field of thing.
On the other hand, the opposed surface on a surface for being stained with carrier film thereon for metal layer can be adhered to polymerization
On resin layer.The example of the metal included in metal layer includes：Metal, such as gold, silver, copper, tin, nickel, aluminium and titanium；With comprising
The alloy of the mixture of two or more in these metals.The thickness of metal layer can be 10nm to 10 μm.If metal layer
Thickness excessively increased to over 10 μm, then excessive metal is needed to form metal layer, so as to increase original material cost simultaneously
Reduce the efficiency of economic aspect.
Carrier film can be adhered to a surface of metal layer.Carrier film can be adhered to a surface of metal layer
With prevent such as move or adhesion metal layer during directly contacted with the surface of metal layer, and adhere to it in metal layer
Afterwards, because it is possible that physics, which is peeled off, it is possible to easily remove carrier film.The instantiation of carrier film does not limit especially
System, and for example, various organic materials and inorganic material can be applied, such as polymer, metal and rubber.At one
In embodiment, material of the material identical with metal layer as carrier film can be preferably used.Therefore, as described below, may be used
Pattern is formed to etch carrier film and metal layer at the same time by identical etchant.
On the other hand, the opposed surface on a surface for being stained with carrier film thereon for metal layer can be adhered to polymerization
Resin layer.The opposed surface on one surface of metal layer means surface parallel and towards it with a surface of metal layer.
When the opposed surface on a surface for being stained with carrier film thereon for metal layer is adhered to polymer resins layers, can be formed
Wherein metal laminate is in polymer resins layers and carrier film laminated structure on the metal layer successively.
In this case, since the bonding force between carrier film and metal layer can be less than polymer resins layers and metal
Bonding force between layer, therefore can prevent polymer resins layers and metal layer during the physics of carrier film and metal layer is peeled off
Stripping, as described later.When the bonding force between polymer resins layers and metal layer is less than between carrier film and metal layer
During bonding force, polymer resins layers and metal layer are stripped during the physics of carrier film and metal layer is peeled off, it is possible that difficult
To form fine pattern in polymer resins layers.
The step of forming patterned photosensitive resin layer on a carrier film
Photosensitive resin layer can be laminated on a carrier film to form figuratum state, or can be in laminated pattern afterwards
Change, but it is highly preferred that pattern can be formed afterwards on a carrier film laminated.
The example of photosensitive resin layer can include photo-conductive film resist (DFR) etc., it is alkali solubility or non-thermosettable.
The step of forming patterned photosensitive resin layer on a carrier film can include making to be formed on a carrier film photosensitive
Resin bed exposes and alkali development.In this case, photosensitive resin layer may be used as the protective layer of carrier film, or as pattern
Change mask.
In the step of forming patterned photosensitive resin layer on a carrier film, photosensitive resin layer on a carrier film is formed
Thickness can be 1 μm to 500 μm, 3 μm to 500 μm, 3 μm to 200 μm, 1 μm to 60 μm or 5 μm to 30 μm.Work as photosensitive resin layer
Thickness when excessively increasing, the resolution ratio of polymer resins layers may be decreased.
In the step of making to be formed the exposure of photosensitive resin layer on a carrier film and alkali development, formed on a carrier film photosensitive
The example of the method for resin bed is not particularly limited, it is, for example, possible to use by membranaceous photosensitive resin such as photo-conductive film resist
Laminated method on a carrier film or by spraying photosensitive resin composition coating or impregnating on a carrier film and suppress painting
Method of overlay film etc..
Make to be formed the exposure of photosensitive resin layer on a carrier film and the step of alkali development in, make photosensitive resin layer exposure with
The example of the method for alkali development is not particularly limited, but for example, can optionally be exposed by the following method：Make to be formed
There is the method that the photomask of predetermined pattern and photosensitive resin layer are contacted and then irradiated with ultraviolet；Made by projection objective in mask
Comprising predetermined pattern imaging then with ultraviolet irradiate method；Make what is included in mask using laser diode as light source
Predetermined pattern direct imaging and then the method irradiated with ultraviolet；Etc..In this case, the example of ultraviolet irradiation condition
It can include using 5mJ/cm2To 600mJ/cm2Light quantity irradiation.
In addition, in the step of making to be formed the exposure of photosensitive resin layer on a carrier film and alkali development, make photosensitive resin layer
The example of the method for development can include the method handled with alkaline developer.The example of alkaline developer is not particularly limited,
But it is, for example, possible to use alkaline aqueous solution, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium metasilicate,
Ammonia, tetramethylammonium hydroxide, amine etc., and preferably, 30 DEG C of 1% sodium carbonate developers can be used.Alkaline developer
Specifically used amount is not particularly limited.
In the case where being handled with alkaline developer, only the part of photosensitive resin layer is removed by development, and under being located at
The polymer resins layers comprising alkali soluble resins and thermal curable binding agent in portion can be protected by carrier film, so as to prevent the layer
Development.Therefore, in the independent step that need not be used to prevent polymer resins layers from developing (for example, making polymer resins layers in advance
The step of curing, or two or more different metal layers are introduced to carry out patterned step successively with different etchants
Suddenly in the case of), by using the fine metal layer being formed on polymeric layer as the similar reduction aspect ratio of Etching mask
The resolution ratio of through hole can be improved.
The carrier film exposed by patterned photosensitive resin layer and metal layer are removed to form the step of patterned metal layer
Suddenly
In the step of removing the carrier film exposed by patterned photosensitive resin layer and metal layer, photosensitive resin figure is used
Case is as the resist for forming pattern in carrier film and metal layer.Therefore, the carrier exposed by photosensitive resin layer pattern
Film and metal layer mean the part that its surface of carrier film and metal layer is not contacted with photosensitive resin layer.
Specifically, the step of removing the carrier film exposed by photosensitive resin layer pattern and metal layer can include wherein etching
The step of agent passes through the photosensitive resin layer with the pattern being formed thereon and is contacted with carrier film and metal layer.
Etchant can be selected according to carrier film and the species of metal layer, further, it is preferred that using to lower part copper wire
Material that is smaller and not influencing photosensitive resin layer is influenced, if possible.
However, as described above, in this embodiment it is preferred to ground uses the material identical with metal layer as carrier film
Material, carrier film and metal layer are sequentially or simultaneously removed from there through identical etchant, and therefore, can be readily formed figure
Case.
On the other hand, the carrier film and metal layer exposed in removing by patterned photosensitive resin layer is patterned to be formed
In the step of metal layer, the gross weight based on polymer resins layers, the removal rate of polymer resins layers can be 0.01 weight %
Or smaller.Phrase " gross weight based on polymer resins layers, the removal rate of polymer resins layers is 0.01 weight % or smaller "
It can mean that the degree that polymer resins layers are removed is not very notable, or polymer resins layers are not removed.
That is, removing the carrier film that is exposed by patterned photosensitive resin layer and metal layer to form patterned metal layer
The step of in the etchant that uses there is no physics and chemical affect at all to polymer resins layers.Therefore, can stably keep
Polymer resins layers are covered until forming fine metal pattern layer by using fine metal pattern layer as resist
Mould can improve the resolution ratio of through hole to reduce aspect ratio.
The step of being separated from patterned metal layer and removing carrier film
Patterned removing the carrier film exposed by patterned photosensitive resin layer and metal layer as described above with being formed
Metal layer the step of after, can make patterned metal layer, patterned carrier film and patterned photosensitive resin layer according to
It is secondary laminated.
At this time, in order to form insulating layer, it is necessary to polymer resins layers and be formed in except eliminating in polymer resins layers
All rest layers outside patterned metal layer.For this reason, routinely, it is used for removing using alkaline developer and is formed for pattern
Photosensitive resin layer.In this case, the problem of making polymer resins layers simultaneously or sequentially develop there are alkaline developer.Separately
Outside, in the case of using the metal layer that pattern is formed is used for, metal layer is removed due to the use of etchant, can occur in which
The problem of such as lower part etching of copper lines.
On the other hand, can be by separating and removing carrier film with metal layer in the case of an embodiment
Straightforward procedure easily rest layers in addition to the patterned metal layer being formed in polymer resins layers is eliminated.
In the above-described embodiment, since the bonding force between carrier film and metal layer is less than polymer resins layers and metal
Bonding force between layer, so can prevent polymer resins layers and metal in the physics stripping process of carrier film and metal layer
The stripping of layer.
In addition, during carrier film is separated with metal layer, due to the carrier film in the state of bonding or stripping and
The photosensitive resin layer formed on a carrier film is removed together, so can also be easy in the case of without using etchant
Ground only stays in fine metal pattern mask in polymer resins layers, and therefore, by patterning process as described below come
The resolution ratio of through hole can be improved by reducing aspect ratio.
The step of making the polymer resins layers alkali development exposed by patterned metal layer
In addition, the polymer resins layers alkali that the method for manufacture insulating layer can include making to be exposed by patterned metal layer is shown
Shadow.By the surface portion of polymer resins layers that is only exposed as described above by forming pattern on the metal layer optionally
The process contacted with alkaline developer, can ensure the precision and higher of phase same level while conventional laser etching method is replaced
Process economics.
In the step of polymer resins layers alkali development for making to be exposed by patterned metal layer, metal layer pattern effect
In the resist that pattern is formed in polymer resins layers.Therefore, the polymer resins layers exposed by metal layer pattern mean to gather
The part that its surface of polymer resin layer is not contacted with metal layer.
Specifically, the step of alloing the polymer resins layers alkali development exposed by patterned metal layer, includes wherein alkali
Property developer the step of passing through with the metal layer of pattern being formed thereon and being contacted with polymer resins layers.
Since polymer resins layers include alkali soluble resins, so it causes it to be dissolved in alkaline developer with alkali solubility
In, cause the part contacted with alkaline developer of polymer resins layers can dissolve and be removed.
On the other hand, after the step of polymer resins layers alkali development for making to be exposed by patterned metal layer, it is based on
The gross weight of the polymer resins layers exposed by patterned metal layer, 0.1 weight % to 85 weight %, 0.1 weight % to 50
Weight % or 0.1 weight % to 10 weight % can be remained.This is considered as because the alkali included in polymer resins layers
Soluble resin is removable by the alkaline developer, but the thermal curable binding agent with small alkaline development characteristic or inorganic filler are protected
Stay and be not removed.
Therefore, when as desired by etching process to remove patterned metal layer, the lower copper that is exposed by pattern
Paper tinsel can be therewith etched, so that etch-back (etch back) minimizes.
Meanwhile it can be removed by using processing such as strippers in the fluoropolymer resin for making to be exposed by patterned metal layer
The polymer resins layers retained after the step of layer alkali development.That is, in the fluoropolymer resin for making to be exposed by patterned metal layer
After the step of layer alkali development, this method can also include the step of being handled with stripper, and the type of stripper and processing
Method is not particularly limited.
Especially, in order to control the degree of inorganic filler and the reservation of thermal curable binding agent, thermosetting binder can be controlled
Agent and inorganic filler are relative to ratio of acidic functionality on the weight ratio of alkali soluble resins, the surface of inorganic filler etc..It is excellent
Selection of land, based on the alkali soluble resins of 100 parts by weight, can add 20 parts by weight to 100 parts by weight thermal curable binding agent and
The inorganic filler of 100 parts by weight to 600 parts by weight.The acid number on the surface of inorganic filler can be 0mgKOH/g to 5mgKOH/g or
0.01mgKOH/g to 5mgKOH/g.Those in the method for acid number of the details of acid number with measuring alkali soluble resins are identical.
The example of alkaline developer is not particularly limited, but it is, for example, possible to use alkaline aqueous solution, such as potassium hydroxide,
Sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, amine etc., and preferably, Ke Yi
1% sodium carbonate developers are used at 30 DEG C.The specifically used amount of alkaline developer is not particularly limited.
Make polymer resins layers heat cure after alkali development the step of
In addition, the method for manufacture insulating layer makes polymer resins layers heat cure after being included in alkali development.Make polymerization
The step of resin layer heat cure, can carry out at a temperature of 100 DEG C to 250 DEG C.
Meanwhile after the step of making polymer resins layers heat cure, this method can also include removing fluoropolymer resin
Metal layer on layer.Removing the method for metal layer can include removing lower part copper wire of the metal layer without removing polymer resins layers
Or the method for only removing its part at the same time.
As instantiation, by making the thickness of copper foil of metal layer extremely thin (3 μm or smaller), in the case where being partially removed in
Metal layer is removed while portion's copper wire, or the etchant for removing metal layer without influencing lower part copper wire can be used.
On the other hand, another embodiment according to the present invention, there is provided for manufacturing the side of multilayer board
Method, forms the step of forming figuratum metal base thereon on its insulating layer for including manufacturing in embodiments.
The inventors discovered that since the insulating layer manufactured in the embodiment above includes certain patterns of openings, by gold
Belong to base material it is new it is laminated on the insulating layer during, is filled with metal in patterns of openings, thus metal below and above
Base material is based on insulating layer and connects, so as to produce multilayer board.Based on the discovery that complete the present invention.
Insulating layer may be used as the interlayer dielectic of multilayer board, and can include alkali soluble resins and can
The cured product of hot setting adhesive.The details of alkali soluble resins and thermal curable binding agent is included described in the embodiment above
Those.If desired, thickness can be formed on the surface of insulating layer as 5 μm or the copper foil layer of smaller.
The step of forming figuratum metal base thereon is formed on the insulating layer to be referred to as semi-additive process (SAP) or changing
The fine circuit pattern forming process of good figure semi-additive process (MSAP).SAP means wherein there is no in the state of anything
Form the process of fine circuit pattern on the insulating layer, MSAP means formed with thickness to be on the insulating layer wherein 5 μm or more
The process of fine circuit pattern is formed in the state of small copper foil.
The more specific examples for forming the step of forming figuratum metal base thereon on the insulating layer comprise the following steps：
Metallic film is formed on the insulating layer；Formed on metallic film and form figuratum photosensitive resin layer thereon；By metal deposit
On the metallic film of the pattern exposure by photosensitive resin layer pattern；Remove photosensitive resin layer；With the metallic film for removing exposure.
In the step of forming metallic film on the insulating layer, the example for forming the method for metallic film is deposited including dry type
Method or wet deposition, and the instantiation of dry deposition includes vacuum deposition, ion plating, sputtering etc..On the other hand, make
For the instantiation of wet deposition, it can be mentioned that the electroless plating of various metals etc., and more specifically, electroless plating can be used
Copper.In addition, roughening processing step can also be included before or after vapour deposition.
In addition, the method for forming metallic film on the insulating layer, embodiment be used for manufacture insulating layer
Method in use metal layer as protective layer in the case of, caused insulating layer can be used as it is.
It can be dry and wet according to condition to be roughened processing procedure.The example of dry method includes application of vacuum, atmospheric pressure
Processing, gas plasma process, gas excimers UV processing etc..The example of wet method includes the Slag treatment that removes photoresist.Pass through this
A little roughening processing procedures, can increase the surface roughness of metallic film and improve the metal with being deposited on metallic film
Adhesiveness.
The step of forming metallic film on the insulating layer is additionally may included in before deposited metal film shape on the insulating layer
The step of into surface-treated layer.It is possible thereby to improve the adhesiveness between metallic film and insulating layer.
Specifically, the example as the method for forming surface-treated layer on the insulating layer, can use and be aided in selected from ion
Any one of reaction method, ion beam processing method and plasma processing method.Plasma processing method can including air etc. from
Any one of daughter facture, DC plasma processing methods and RF plasma processing methods.Knot as surface treatment process
Fruit, can form the surface-treated layer for including reactive functional groups on the surface of insulating layer.As forming table on the insulating layer
Another example of the method for surface treatment layer, it can be mentioned that deposit thickness is the chromium of 50nm to 300nm on the surface of insulating layer
(Cr) and titanium (Ti) metal method.
Meanwhile it can include making to be formed in forming the step of being formed with the photosensitive resin layer of pattern on metallic film
The exposed and developed step of photosensitive resin layer on metallic film.Photosensitive resin layer, exposed and developed details can include upper
Those in the embodiment stated.
In step on the metallic film exposed by photosensitive resin layer pattern is deposited metal in, by photosensitive resin layer figure
The metallic film of case exposure means the part not contacted in metallic film with the photosensitive resin layer on surface.Metal to be deposited can
Think copper.The example of deposition process is not particularly limited, and can without limitation using it is various it is known physically or chemically
CVD method.As general example, copper electroplating method can be used.
In the step of removing photosensitive resin layer and removing the metallic film of exposure, the method for photosensitive resin layer is being removed
Photoresist stripper can be used in example, in the removing due to photosensitive resin layer and the removing side of the metallic film of exposure
Etchant can be used in the example of method.
The multilayer board manufactured by the manufacture method of multilayer board can again act as laminated material.
For example, the manufacture method that can repeatedly carry out insulating layer according to an embodiment is formed absolutely on multilayer board
The first step of edge layer, and formed on the insulating layer according to the manufacture method of the multilayer board of another embodiment
The second step of metal base.
Therefore, the layer by including for manufacturing the multilayer board manufactured by the method for multilayer board
The number for closing layer is not particularly limited, and according to application purpose and purposes, it can have such as one to 20 layer.
Beneficial effect
According to the present invention it is possible to the method for manufacturing insulating layer is provided, its effect in terms of cost and productivity is improved
Uniform and fine pattern can be realized while rate, and may also be ensured that excellent mechanical property；And use is by manufacturing
Insulating layer that the method for insulating layer obtains manufactures the method for multilayer board.
Brief description of the drawings
Fig. 1 schematically shows the manufacturing process of the insulating layer of embodiment 1.
Fig. 2 schematically shows the manufacturing process of the multilayer board of embodiment 2.
Embodiment
Hereinafter, the present invention will be more fully described by embodiment.But, there is provided these embodiments are only used for illustrating
Purpose, and the scope that should not be construed as limiting the invention.
<Preparation example：The preparation of alkali soluble resins>
Preparation example 1
With heating and cooling capacity and equipped with thermometer, blender, reflux condenser and quantitative psychrometrc analysis
The maleimide that 632g substitutes as dimethylformamide (DMF), the 358g of solvent as N- is put into 2 liters of reaction vessels of device
4- aminophenyl acetic acids of the BMI-1100 (ProductName, is manufactured by Daiwakasei) and 151g of amine compounds as amine compounds
And mix, when stirring 24 is small at 85 DEG C, to prepare solids content as 50% alkali soluble resins solution.
Preparation example 2
With heating and cooling capacity and equipped with thermometer, blender, reflux condenser and quantitative psychrometrc analysis
The maleimide that 632g substitutes as dimethylformamide (DMF), the 434g of solvent as N- is put into 2 liters of reaction vessels of device
Amine compounds as 4, the 4- diaminodiphenyl-methanes of amine compounds and mix carboxy phenyl maleimide and 198g,
When stirring 24 is small at 85 DEG C, to prepare solids content as 50% alkali soluble resins solution.
Preparation example 3
With heating and cooling capacity and equipped with thermometer, blender, reflux condenser and quantitative psychrometrc analysis
543g is put into 2 liters of reaction vessels of device as the dimethylacetylamide (DMAc) of solvent and is mixed, adds 350g thereto
SMA1000 (Cray Valley), 144g 4-aminobenzoic acid (PABA) and 49g 4-aminophenol (PAP) simultaneously mix.In nitrogen
After the temperature of reactor is set as 80 DEG C under atmosphere, make when acid anhydrides and small anil reaction 24 to form amic acid.
Then, after the temperature of reactor is set as 150 DEG C, continue imidization reaction 24 it is small when, contained with preparing solid
Measure the alkali soluble resins solution for 50%.
Preparation example 4
With heating and cooling capacity and equipped with thermometer, blender, reflux condenser and quantitative psychrometrc analysis
516g is put into 2 liters of reaction vessels of device as the methyl ethyl ketone (MEK) of solvent and is mixed, 228g is to carboxy phenyl Malaysia for addition
Acid imide, 85g p-hydroxyphenyls maleimide, 203g styrene and 0.12g azodiisobutyronitriles (AIBN) simultaneously mix.In nitrogen
The temperature of reactor is gradually risen to after 70 DEG C under atmosphere, continue reaction 24 it is small when, to prepare solids content as 50%
Alkali soluble resins solution.
<Embodiment 1：The manufacture of insulating layer>
With reference to Fig. 1, by by regarding the alkali soluble resins synthesized in 16g preparation examples 1,5g as thermal curable binding agent
MY-510 (being manufactured by Huntsman) and 35g is obtained as SC2050MTO (being manufactured by the Adamatech) mixing of inorganic filler
Polymer resin composition be coated on being stained with extra thin copper foil 4MT18SD-H that the thickness of carrier copper foil 5 is 3 μm (by
Mitsui Kinzoku are manufactured) on and it is dry to prepare thickness as 15 μm of polymer resins layers 1.Then, will be poly- at 85 DEG C
1 vacuum laminated of polymer resin layer is wherein on the circuit board formed with copper wire 2 on copper foil lamilate 3, by thickness at 110 DEG C
It is laminated in for 15 μm of photo-conductive film resist KL 1015 (being manufactured by Kolon Industries) 6 on carrier copper foil 5.
A diameter of 30 μm of circular negative photomask is contacted with photo-conductive film resist 6, and (25mJ/ is irradiated with ultraviolet
cm2Light quantity).Then, dry film photoresist 6 is made to be developed to certain pattern by 1% sodium carbonate developers at 30 DEG C.
Then, carrier copper foil 5 and extra thin copper foil 4 are etched by using etchant process.At this time, figuratum light is formed thereon
Quick dry film photoresist 6 serves as the protective layer of carrier copper foil 5 and extra thin copper foil 4 so that or even in carrier copper foil 5 and extra thin copper foil 4
In also form the pattern identical with photo-conductive film resist 6.
Then, extra thin copper foil 4 is made to be separated with carrier copper foil 5 so that carrier copper foil 5 and the light being laminated on carrier copper foil 5
Quick dry film photoresist 6 is removed.
Then, polymer resins layers 1 are made to develop by 1% sodium carbonate developers at 30 DEG C.At this time, thereon formed with figure
The extra thin copper foil 4 of case serves as the protective layer of polymer resins layers 1 so that while the pattern identical with extra thin copper foil 4 is formed
Through hole 7 is also even formed in polymer resins layers 1.
Then, when progress heat cure 1 is small at a temperature of 110 DEG C, then with etchant process to remove extra thin copper foil 4,
And further carried out at a temperature of 200 DEG C curing process 1 it is small when to produce insulating layer.
<Embodiment 2：The manufacture of multilayer board>
With reference to Fig. 2, by sputtering method, in the upper surface of the insulating layer 1 manufactured with vapor deposition apparatus into embodiment 1 and
Through hole 7 side surface supply argon and oxygen mixed gas while, with thickness titanium deposition (Ti) metal of 50nm and with 0.5 μm
Thickness deposits (Cu) to form Seed Layer 8.
Then, make photosensitive resin layer exposed and developed in Seed Layer 8 to form photosensitive resin pattern 9.Then, electricity is passed through
Solution is plated in the metal base 10 for being formed and being made of copper in Seed Layer 8.Then, photosensitive resin figure is removed using photosensitive resin stripper
Case 9, so as to remove the Seed Layer 8 of exposure by etching, thus produces multilayer board.
<Embodiment 3：The manufacture of insulating layer>
Insulating layer is manufactured in the same manner as in example 1, and difference is the manufacture in the insulating layer of embodiment 1
The alkali soluble resins synthesized in preparation example 2 is used to replace the alkali soluble resins synthesized in preparation example 1 in method.
<Embodiment 4：The manufacture of insulating layer>
Insulating layer is manufactured in the same manner as in example 1, and difference is the manufacture in the insulating layer of embodiment 1
The alkali soluble resins synthesized in preparation example 3 is used to replace the alkali soluble resins synthesized in preparation example 1 in method.
<Embodiment 5：The manufacture of insulating layer>
Insulating layer is manufactured in the same manner as in example 1, and difference is the manufacture in the insulating layer of embodiment 1
The alkali soluble resins synthesized in preparation example 4 is used to replace the alkali soluble resins synthesized in preparation example 1 in method.
<Comparative example 1：The manufacture of insulating layer>
By by MY-510 that the alkali soluble resins synthesized in 16g preparation examples 1,5g are used as to thermal curable binding agent (by
Huntsman is manufactured) and 35g mixed and the polymer that obtains as the SC 2050MTO (being manufactured by Adamatech) of inorganic filler
Resin composition is on PET film (25 μm) and dry to prepare thickness as 15 μm of polymer resins layers 1.Then, 85
At DEG C by 1 vacuum laminated of polymer resins layers wherein on the circuit board formed with copper wire 2 on copper foil lamilate 3, and remove
PET film.
The photo-conductive film resist KL 1015 that thickness is 15 μm (is manufactured into) layer by KolonIndustries at 110 DEG C
Close in polymer resins layers.A diameter of 30 μm of circular negative photomask is contacted with photo-conductive film resist, and use ultraviolet
(25mJ/cm2Light quantity) irradiation.Then, photo-conductive film resist and polymer are made by 1% sodium carbonate developers at 30 DEG C
Resin bed develops successively.
At this time, photo-conductive film resist serves as the protective layer of polymer resins layers, and against corrosion with photo-conductive film being formed
Through hole is also even formed in polymer resins layers while agent identical pattern.
Then, when progress heat cure 1 is small at a temperature of 100 DEG C, then handled with 3% sodium hydroxide anticorrosive additive stripping liquid controlling
To remove photo-conductive film resist, and further carried out at a temperature of 200 DEG C heat cure 1 it is small when to produce insulating layer.
<Comparative example 2：The manufacture of multilayer board>
Multilayer board is manufactured in a manner of in the same manner as in Example 2, difference is made in using comparative example 1
The insulating layer made replaces the insulating layer manufactured in embodiment 1.
<Experimental example：The measurement of the physical characteristic of the insulating layer obtained in embodiment and comparative example>
The physical characteristic of the insulating layer obtained in above-described embodiment and comparative example is measured by the following method, as a result in following table
Shown in 1.
1. through-hole diameter
The upper shed that the insulating layer obtained in embodiment 1 and 3 to 7 and comparative example 1 is measured using light microscope is (logical
Hole) diameter.
2. the metal bonding force as caused by hygroscopicity
135 DEG C and 85% moisture absorption under stand the multilayer board that is obtained in embodiment 2 and comparative example 2
48 it is small when, then according to the peel strength of IPC-TM-650 canonical measure metals.It is derived from metal bonding force.
3. height accelerates temperature and humidity stress test (HAST) patience
The multilayer board for determining to obtain in embodiment 2 and comparative example 2 according to the standard of JESD 22-A101
HAST patience.Specifically, it is 50 μm to width, applies the electricity of 3V at intervals of the circuit board for the test block that 50 μm and thickness are 12 μm
Pressure, be then allowed to rest for 168 it is small when, the circuit board for then determining test block according to following standard whether there is abnormal appearance.
OK：Exception is not observed in film outward appearance
NG：Bubble and stripping are observed in film
【Table 1】
The result of the experimental example of embodiment and comparative example
| Classification | Through-hole diameter (μm) | Metal adhesion (kgf/cm) | HAST characteristics (μm) |
| Embodiment 1 | 32 | - | - |
| Embodiment 2 | - | 0.4 | OK |
| Embodiment 3 | 33 | - | - |
| Embodiment 4 | 33 | - | - |
| Embodiment 5 | 32 | - | - |
| Comparative example 1 | 45 | - | - |
| Comparative example 2 | - | 0.3 | OK |
As shown in table 1, in comparative example 1 wherein using only photo-conductive film the insulating layer of through hole is formed as protective layer
In the case of, the diameter of through hole is shown as 45 μm, and the diameter of the through hole included in the insulating layer manufactured in embodiment 1 and 3 to 5 subtracts
As low as 32 μm or 33 μm.It is possible thereby to determine, in the case of the embodiment, it is possible to achieve finer pattern.
Furthermore, it is possible to determine, in the situation of the multilayer board of the comparative example 2 of the insulating layer acquisition by comparative example 1
Under, metal bonding force is measured as 0.3kgf/cm, and in the case of the multilayer board of embodiment 2, metal bonding force is surveyed
Measure to be up to 0.4kgf/cm, so as to improve the interfacial adhesion between insulating layer and conductive layer, and show excellent
HAST patience.
【Description of reference numerals】
1：Polymer resins layers
2：Copper wire
3：Copper foil lamilate
4：Extra thin copper foil
5：Carrier copper foil
6：Photo-conductive film resist (DFR)
7：Through hole
8：Seed Layer
9：Photosensitive resin pattern
10：Metal base
<1>Extremely<8>：The progress order of method
Claims (20)
1. a kind of method for manufacturing insulating layer, comprises the following steps：
The opposed surface for the metal layer that carrier film is stained with one surface is adhered to comprising alkali soluble resins and can thermosetting
In the polymer resins layers for changing binding agent；
Patterned photosensitive resin layer is formed in the carrier film；
The carrier film and the metal layer by the patterned photosensitive resin layer exposure are removed to form patterned gold
Belong to layer；
Separated from the patterned metal layer and remove the carrier film；
Make by the polymer resins layers alkali development of the patterned metal layer exposure；And
Make the polymer resins layers heat cure after the alkali development.
2. the method according to claim 1 for manufacturing insulating layer, wherein carrier will be stained with one surface
The opposed surface of the metal layer of film adheres to the step in the polymer resins layers comprising alkali soluble resins and thermal curable binding agent
In rapid, the bonding force between the carrier film and the metal layer is less than between the polymer resins layers and the metal layer
Bonding force.
3. the method according to claim 1 for manufacturing insulating layer, wherein dividing from the patterned metal layer
From and the step of remove the carrier film in, the carrier film and the photosensitive resin layer that is formed in the carrier film are by one
Rise and remove.
4. the method according to claim 1 for manufacturing insulating layer, wherein removing by the patterned photosensitive tree
In the step of carrier film of lipid layer exposure and the metal layer are to form patterned metal layer, pass through identical etchant
Remove successively or remove the carrier film and the metal layer at the same time.
5. the method according to claim 1 for manufacturing insulating layer, wherein removing by the patterned photosensitive tree
In the step of carrier film of lipid layer exposure and the metal layer are to form patterned metal layer, based on the polymer tree
The gross weight of lipid layer, the removal rate of the polymer resins layers is 0.01 weight % or smaller.
6. the method according to claim 1 for manufacturing insulating layer, wherein being formed in the carrier film patterned
The step of the step of photosensitive resin layer, is including making to be formed in the exposure of the photosensitive resin layer in the carrier film and alkali development.
7. the method according to claim 6 for manufacturing insulating layer, wherein making to be formed in the institute in the carrier film
In the step of stating photosensitive resin layer exposure and alkali development, the polymer resins layers are protected by the carrier film.
8. the method according to claim 1 for manufacturing insulating layer, wherein making the polymer resins layers heat cure
The step of after, the method can also include removing the metal layer in the polymer resins layers.
9. the method according to claim 1 for manufacturing insulating layer, wherein the alkali soluble resins includes at least one
Acidic functionality and at least one cyclic imide functional group substituted through amino.
10. the method according to claim 9 for manufacturing insulating layer, wherein the cyclic imide substituted through amino
Functional group includes the functional group represented by formula 1 below：
[chemical formula 1]
Wherein, in chemical formula 1, R1Mean bonding point for alkylidene or alkenyl with 1 to 10 carbon atom, and " * ".
11. the method according to claim 9 for manufacturing insulating layer, wherein the alkali soluble resins passes through ring-type insatiable hunger
Reaction with imide compound and amine compounds and produce, and the ring-type unsaturated acyl group with imine moiety and the amination
At least one of compound is included in the acidic functionality of its end substitution.
12. the method according to claim 11 for manufacturing insulating layer, wherein the amine compounds include being selected from through ammonia
At least one of the carboxylic acid compound of base substitution and the multi-functional amine compounds containing two or more amino.
13. the method according to claim 1 for manufacturing insulating layer, wherein the alkali soluble resins includes at least one
The repetitive unit and at least one repetitive unit represented by formula 4 below represented by formula 3 below：
[chemical formula 3]
Wherein, in chemical formula 3, R2Alkylidene for direct key, with 1 to 20 carbon atom, with 1 to 20 carbon atom
Alkenyl or the arlydene with 6 to 20 carbon atoms, and " * " mean bonding point,
[chemical formula 4]
Wherein, in chemical formula 4, R3Alkylidene for direct key, with 1 to 20 carbon atom, with 1 to 20 carbon atom
Alkenyl or the arlydene with 6 to 20 carbon atoms,
R4For-H ,-OH ,-NR5R6, halogen or the alkyl with 1 to 20 carbon atom,
R5And R6Hydrogen, the alkyl with 1 to 20 carbon atom or the aryl with 6 to 20 carbon atoms can be each independently,
And
" * " means bonding point.
14. the method according to claim 13 for manufacturing insulating layer, wherein the alkali soluble resins is included by making
Represented by the polymer of the repetitive unit of formula 5 below expression, the amine represented by formula 6 below and by formula 7 below
Amine reaction and produce：
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
Wherein, in chemical formula 5 to 7, R2To R4It is identical with those limited in claim 13, and " * " mean bonding point.
15. the method according to claim 13 for manufacturing insulating layer, wherein the alkali soluble resins by make by with
The compound and reacted by the compound of formula 9 below expression and produced that lower chemical formula 8 represents：
[chemical formula 8]
[chemical formula 9]
Wherein, in chemical formula 8 and 9, R2To R4It is identical with those limited in claim 13.
16. the method according to claim 1 for manufacturing insulating layer, wherein the alkali soluble resins passes through KOH drops
Fixed measured acid number is 50mgKOH/g to 250mgKOH/g.
17. the method according to claim 1 for manufacturing insulating layer, wherein the alkali solubility based on 100 parts by weight
Resin, the polymer resins layers include thermal curable binding agent of the amount for 1 parts by weight to 150 parts by weight.
18. the method according to claim 1 for manufacturing insulating layer, is selected from wherein the thermal curable binding agent includes
Oxetanyl, cyclic ether group, cyclic thioether base, cyanide-based, dimaleoyl imino and benzoAt least one in piperazine base
Kind functional group and epoxy group.
19. the method according to claim 1 for manufacturing insulating layer, is selected from wherein the polymer resins layers also include
At least one of thermal curing catalyst, inorganic filler, levelling agent, dispersant, releasing agent and metal adhesion promoters additive.
20. a kind of method for manufacturing multilayer board, is included in what is manufactured according to any one of claim 1 to 19
The step of forming figuratum metal base thereon is formed on insulating layer.
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| KR20160101419 | 2016-08-09 | ||
| KR10-2016-0101419 | 2016-08-09 | ||
| KR10-2017-0096355 | 2017-07-28 | ||
| KR1020170096355A KR101947150B1 (en) | 2016-08-09 | 2017-07-28 | Method for manufacturing insulating film and multilayered printed circuit board |
| PCT/KR2017/008247 WO2018030694A1 (en) | 2016-08-09 | 2017-07-31 | Insulating layer manufacturing method and multilayered printed circuit board manufacturing method |
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| CN111656874A (en) * | 2018-09-20 | 2020-09-11 | 株式会社Lg化学 | Multilayer printed circuit board, method for manufacturing the same, and semiconductor device using the same |
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| JP2021017454A (en) * | 2019-07-17 | 2021-02-15 | 住友ベークライト株式会社 | Polymer production method, polymer-containing composition, and polymer |
| JP7325891B2 (en) * | 2019-10-24 | 2023-08-15 | エルジー・ケム・リミテッド | Insulating layer for multi-layer printed circuit board, multi-layer printed circuit board including the same, and manufacturing method thereof |
| TWI795012B (en) * | 2021-10-05 | 2023-03-01 | 艾姆勒科技股份有限公司 | Substrate structure having thick conductive layer and method for etching the same |
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| CN107926124B (en) | 2020-07-03 |
| KR20180018333A (en) | 2018-02-21 |
| TWI630224B (en) | 2018-07-21 |
| JP2018530167A (en) | 2018-10-11 |
| TW201823304A (en) | 2018-07-01 |
| JP6600088B2 (en) | 2019-10-30 |
| KR101947150B1 (en) | 2019-02-12 |
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