CN1701953A - Flexible metal clad laminate film and a manufacturing method for the same - Google Patents

Flexible metal clad laminate film and a manufacturing method for the same Download PDF

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Publication number
CN1701953A
CN1701953A CNA2004100864325A CN200410086432A CN1701953A CN 1701953 A CN1701953 A CN 1701953A CN A2004100864325 A CNA2004100864325 A CN A2004100864325A CN 200410086432 A CN200410086432 A CN 200410086432A CN 1701953 A CN1701953 A CN 1701953A
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申东天
卞廷日
李濬熙
姜炳彦
李坰埈
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LS Corp
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LG Cable Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a flexible metal clad laminate film and a manufacturing method for the same. The flexible metal clad laminate film of the present invention comprises a metal thin film; and a flexible insulating film formed by photo-crosslinking reaction of photoactive polymers having photoactive side chains, which may be crosslinked by photo-irradiation. The flexible metal clad laminate film of the present invention has good physical properties such as size stability, and is almost not deflected or twisted, since it includes the flexible insulating film composed of crosslinked resin formed by photo-crosslinking reaction of photoactive polymer.

Description

Flexible metal clad laminate film and preparation method thereof
Technical field
The present invention relates to a kind of flexible metal clad laminate film and preparation method thereof.
Background technology
Recently, along with the microminiaturization of electronic product, highly integrated, simplification and high performance, a kind of flexible PCB based on flexible metal clad laminate film (FCB) has caused that people's attention, sort circuit plate have thin, soft light characteristics.
This flexible metal clad laminate film is formed in the form of lamination flexible base film on the conductive metal film such as copper and aluminium for example.In addition, between flexible base film and metallic film, can use adhesive.That is to say that the structure of flexible metal clad laminate film is, the structure more than 3 layers or 3 layers that it is made up of flexible base film-adhesive-metallic film, or the structure of forming by flexible base film-metallic film more than 2 layers or 2 layers.
The flexible base film of flexible metal clad laminate film is made up of organic polymer material, as polymer such as polyimides, polyamide, polyester, polysulfones and polyethers-acid imides.This flexible base film should have physical properties such as insulating properties, heat-resisting quantity, chemical resistance, dimensional stability, dielectricity, mechanical strength, solvent resistance, welding stability.
Yet,,, have problems such as easy deformation and warpage if use in flexible metal clad laminate film because the linear expansion coefficient of traditional flexible base film is bigger usually.In addition, physical properties such as its dimensional stability, hear resistance, dielectricity are also unsatisfactory.
Summary of the invention
The present invention proposes for the problem that solves the prior art existence, therefore, an object of the present invention is to provide a kind of flexible metal clad laminate film of forming by metallic film and flexible insulating film, described flexible insulating film is made through photo-crosslinking by the photosensitive polymer with photosensitive side chain, and wherein photosensitive side chain can be undertaken crosslinked by light radiation.
Another object of the present invention provides a kind of method of producing flexible metal clad laminate film, said method comprising the steps of: but preparation has the photosensitive polymer of the crosslinked photosensitive side chain of light radiation; With the prepared photosensitive polymer of a kind of dissolution with solvents, obtain photosensitive polymer solution; Described solution is coated in the metallic film surface, thereby forms coating; Remove the solvent in the coating; Irradiation removes the coating surface that desolvates, so that photosensitive polymer is crosslinked, thereby forms flexible insulating film.
Another object of the present invention provides a kind of method of producing flexible metal clad laminate film, said method comprising the steps of: but preparation has the photosensitive polymer of the crosslinked photosensitive side chain of light radiation; With the prepared photosensitive polymer of a kind of dissolution with solvents, obtain photosensitive polymer solution; Described solution is coated in substrate surface, thereby forms coating; Remove the solvent in the coating; Irradiation removes the coating surface that desolvates, so that photosensitive polymer is crosslinked, thereby forms flexible insulating film; Flexible insulating film is peeled off from substrate surface; Flexible insulating film and metallic film under will peeling off with adhesive are bonded together.
The specific embodiment
Below flexible metal clad laminate film and preparation method thereof among the present invention will be described in more detail.
At first, term in present disclosure and the claim and noun should not be construed as the implication that only limits in common implication or the dictionary, they also have implication and the notion that adapts to the technology of the present invention content, and this is because in order to describe the present invention better, the inventor has suitably defined the notion of some terms.
In the present disclosure,, show then that it can be connected on this ring not contain on the substituent carbon atom arbitrarily if the used straight line of substituting group passes any circulus such as phenyl in the chemical formula.That is to say, it can be positioned at respect to ring go up fixing substituent neighbour, or contraposition.
Flexible metal clad laminate film of the present invention comprises metallic film and the flexible insulating film that is layered on this metallic film.
Herein, according to having or not adhesive phase between metallic film and the flexible insulating film, it can be two-layer or three-decker.
Flexible insulating film is obtained through photo-crosslinking by photosensitive polymer, but this polymer has the crosslinked photosensitive side chain of light radiation.Photosensitive side chain can reaction under the light of specific wavelength such as ultraviolet ray irradiation, so can comprise the cross-linking reaction of photodimerization and photo-crosslinking between the polymer chain.Photosensitive side chain is including, but not limited to alkene derivatives or alkynes derivative, as cinnamate, chalcone, cumarin and maleimide etc.
Crosslinked can formation between the polymer chain by the cycloaddition between the photosensitive side chain of light such as for example ultraviolet ray irradiation initiation.The example of some photo-crosslinkings is seen following reaction equation 1:
Reaction equation 1
The light reaction of cinnamate group
[2+2] cycloaddition reaction forms cyclobutanone
Figure A20041008643200752
The light reaction of chalcone group
[2+2] cycloaddition reaction forms cyclobutanone
The light reaction of cumarin
[2+2] cycloaddition reaction
Figure A20041008643200761
The light reaction of maleimide
[2+2] cycloaddition reaction
Among the present invention, photosensitive polymer preferably has the excellent properties that comprises good heat resistance.Such as, photosensitive polymer is including, but not limited to paracyanogen urate, polyamide-imides, polyester, poly-(sulphur) ether and polyimides etc.Especially, more preferably introduced the photosensitive polymer of triazine ring in the main chain, because this polymer has physical properties such as good hear resistance, dielectricity.Reason is that triazine ring contains three nitrogen-atoms, therefore has good electrophilic.
In addition, because triazine ring can also promote to contain the photo-crosslinking between the side chain of photosensitive functional group, therefore, the present invention more preferably introduces the photosensitive polymer of triazine ring on the main chain, has the photosensitive side chain that photo-crosslinking can take place through light radiation on the described triazine ring.The number-average molecular weight of photosensitive polymer (Mn) preferably 1,000～1,000,000 among the present invention.In addition, by preferred 1 nanometer to 10 of thickness of the flexible insulating film of this photosensitive polymer preparation centimetre.
Metallic film is preferably made by copper, platinum, gold, silver and aluminium etc. among the present invention, but is not limited to these metals.Especially, the more preferably good copper of cost performance.General about 0.1～500 micron of the thickness of metallic film.
Simultaneously, the flexible metal clad laminate film among the present invention can also comprise adhesive phase.The adhesive that is used to prepare flexible metal clad laminate film generally can adopt but be not limited to as based on acrylic acid, based on silicon and based on the adhesive of epoxide etc.
As mentioned above, because the flexible metal clad laminate film among the present invention has flexible insulating film, this dielectric film is made by well behaved photocrosslinkable polymer, so physical property such as its dimensional stability is improved, and warpage and metaboly reduce simultaneously.
Below will describe several preferred photosensitive polymer of introducing on the main chain with the triazine ring of photosensitive side chain in detail, with this example as formation flexible insulating film of the present invention.
The light sensitivity paracyanogen urate polymer that preferably has following Chemical formula 1 among the present invention.
Chemical formula 1
Figure A20041008643200771
In the Chemical formula 1, m+n=1,0≤m≤1,0≤n≤1, R 1Be respectively (1a), (2a) that from following Chemical formula 2, select, (3a) and (4a) group,
Chemical formula 2
??
Figure A20041008643200773
(1a)??????????????????????????????????????(2a)
??
Figure A20041008643200775
(3a)???????????????????????????????????????(4a)
Wherein, the X in the Chemical formula 2 (1a) is selected from the structure of following chemical formula 3,
Chemical formula 3
-((CH 2) nO) m-?????????????????????????????-O((CH 2) nO) m-
Figure A20041008643200781
Figure A20041008643200782
Figure A20041008643200784
Figure A20041008643200785
Figure A20041008643200786
In the chemical formula 3, m and n are respectively 0～10.
In the Chemical formula 2 (1a), Y is selected from the structure of following chemical formula 4,
Chemical formula 4
Figure A20041008643200791
?
Figure A20041008643200792
?
Figure A20041008643200793
???
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively,
Chemical formula 5
-A?-(CA 2) nCA 3?-O(CA 2) nCA 3?-(O(CA 2) m) nCA 3?-O(CA 2) nOCA 3?-(O(CA 2) m) nOCA 3
Figure A20041008643200796
? ???
Figure A20041008643200798
Figure A20041008643200799
?
Figure A200410086432007910
?
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, CI, CN, CF 3And CH 3The group of forming.
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively,
Chemical formula 6
-A?-(CA 2) nCA 3?-O(CA 2) nCA 3?-(O(CA 2) m) nCA 3?-O(CA 2) nOCA 3?-(O(CA 2) m) nOCA 3
Figure A20041008643200801
Figure A20041008643200802
Figure A20041008643200803
Figure A20041008643200804
Figure A20041008643200806
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming.
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7,
Chemical formula 7
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), 1 and 2 are selected from the structure of following chemical formula 8 respectively,
Chemical formula 8
-A
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 1, R 2And R 3Be selected from the structure of following chemical formula 9 respectively,
Chemical formula 9
Figure A20041008643200812
Figure A20041008643200814
Figure A20041008643200816
Figure A20041008643200818
Figure A200410086432008111
In the chemical formula 9, m and n are respectively 0～10, and numeral 1,2,3,4,5,6,7 and 8 is selected from respectively by H, F, Cl, CN, CH 3, OCH 3And CF 3The group of forming, X is selected from H, F, Cl, CN, CH 3, OCH 3Or CF 3, and Y is selected from CH 2, C (CH 3) 2, C (CF 3) 2, O, S, SO 2, CO and CO 2
Among the present invention, preferably has the photosensitive polyester polymers of the structure of following Chemical formula 10.
Chemical formula 10
In the Chemical formula 10, m+n=1,0≤m≤1,0≤n≤1, light sensitivity side chain R 1Be selected from (1a), (2a) in the above-mentioned Chemical formula 2, (3a) or (4a) respectively.Here the explanation of Chemical formula 2 is consistent with above-mentioned chemical formula 3～8.
In the Chemical formula 10, ester bond is formed by the reaction of the alcohol and carboxylic acid shown in the following reaction equation 2.
Reaction equation 2
In the Chemical formula 10, R 4And R 5Be selected from the structure of following Chemical formula 11 respectively.
Chemical formula 11
-(CA 2) nO-??????????????????????????????????????-O((CA 2) nO) m-
Figure A20041008643200835
Figure A20041008643200836
Figure A200410086432008311
In the Chemical formula 11, m and n are respectively 0～10, and A and numeral 1,2,3,4,5,6,7 and 8 are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming.
In the Chemical formula 10, R 6And R 7Be selected from the structure of following Chemical formula 12 respectively,
Chemical formula 12
Figure A20041008643200843
Figure A20041008643200845
Figure A20041008643200846
Figure A20041008643200848
Figure A20041008643200849
Figure A200410086432008410
In the Chemical formula 12, m and n are respectively 0～10.
Poly-(sulphur) ether polymer of light sensitivity that preferably has the structure of following Chemical formula 13 among the present invention.
Chemical formula 13
Figure A200410086432008411
In the Chemical formula 13, m+n=1,0≤m≤1,0≤n≤1, light sensitivity side chain R 1Be selected from (1a), (2a) in the above Chemical formula 2, (3a) or (4a) respectively.The explanation of Chemical formula 2 herein is consistent with above-mentioned chemical formula 3～8.
Ehter bond in the Chemical formula 13 is formed by dihalide and the diol reaction shown in the following reaction equation 3.
Reaction equation 3
Figure A20041008643200851
In addition, the thioether bond in the Chemical formula 13 is formed by dihalide and two thiol reactants shown in the following reaction equation 4,
Reaction equation 4
Figure A20041008643200852
In the Chemical formula 13, R 8And R 9Be selected from the structure in the following Chemical formula 14 respectively,
Chemical formula 14
-(CA 2) n-??????????????????????????????????????????????-O(CA 2) n-
Figure A20041008643200853
Figure A20041008643200855
Figure A20041008643200858
Figure A20041008643200859
Figure A200410086432008510
Figure A20041008643200863
Figure A20041008643200864
Figure A20041008643200865
In the Chemical formula 14, m and n are respectively 0～10, and A and numeral 1,2,3,4,5,6,7 and 8 are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming.
In the Chemical formula 13, R 10And R 11Be selected from the structure of following Chemical formula 15 respectively.
Chemical formula 15
-O(CA 2) nO-???????????????????????????????????-O((CA 2) mO) nO-
Figure A20041008643200867
Figure A20041008643200869
Figure A20041008643200876
Figure A20041008643200877
-S(CA 2) nS-???????????????????????????????????????-S((CA 2) mO) nS-
Figure A200410086432008711
Figure A200410086432008712
Figure A200410086432008713
Figure A20041008643200883
Figure A20041008643200884
Figure A20041008643200889
Figure A200410086432008811
Figure A200410086432008812
In the Chemical formula 15, m and n are respectively 0～10, and A and numeral 1,2,3,4,5,6,7 and 8 are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming.
Among the present invention, preferably has the photosensitive polyamide-acid imide of the structure of following Chemical formula 16.
Chemical formula 16
In the Chemical formula 16, m+n=1,0≤m≤1,0≤n≤1, light sensitivity side chain R 1Be selected from (1a), (2a) in the above-mentioned Chemical formula 2, (3a) or (4a) respectively.Herein, the explanation of Chemical formula 2 is consistent with aforementioned chemical formula 3～8.
In the Chemical formula 16, imide bond is formed by amine shown in the following reaction equation 5 and carboxylic acid dianhydride reaction.
Reaction equation 5
In addition, the imide bond in the Chemical formula 16 is formed by amine and the carboxylic acid reaction shown in the following reaction equation 6.
Reaction equation 6
Figure A20041008643200893
In the Chemical formula 16, R 12And R 13Respectively based on amine with the structure that is selected from following Chemical formula 17.
Chemical formula 17
-(CH 2) n-NH 2???????????????????????????????????-O(CH 2) n-NH 2
Figure A20041008643200901
Figure A20041008643200902
Figure A20041008643200903
Figure A20041008643200905
In the Chemical formula 17, m and n are respectively 0～10.
In addition, in the Chemical formula 16, R 14Respectively based on carboxylic acid dianhydride with the structure that is selected from following Chemical formula 18.
Chemical formula 18
In the Chemical formula 16, R 15Be selected from the structure of following Chemical formula 19,
Chemical formula 19
Figure A20041008643200912
Figure A20041008643200913
Figure A20041008643200918
In the Chemical formula 19, m and n are respectively 0～10.
Among the present invention, preferably has the photo-sensistive polyimide of the structure of following Chemical formula 20.
Chemical formula 20
Figure A20041008643200919
In the Chemical formula 20, m+n=1,0≤m≤1,0≤n≤1, light sensitivity side chain R 1Be selected from (1a), (2a) in the above-mentioned Chemical formula 2, (3a) or (4a) respectively.Herein, the explanation of Chemical formula 2 is consistent with above-mentioned chemical formula 3～8
In the Chemical formula 20, imide bond is formed by amine shown in the above-mentioned reaction equation 5 and carboxylic acid dianhydride reaction.
In the Chemical formula 20, R 16And R 17Respectively based on amine with the structure that is selected from above-mentioned Chemical formula 17.In addition, R 18And R 19Respectively based on carboxylic acid dianhydride with the structure that is selected from above-mentioned Chemical formula 18.
Below will describe the several method of preparation flexible metal clad laminate film among the present invention by way of example in detail.
At first prepare photosensitive polymers.Photosensitive polymers can adopt the synthetic conventional method preparation of polymer.Such as, but be not limited to, can synthesize the monomer that has light sensitivity functional group and reactive functional groups simultaneously, as amine, (sulphur) alcohol, halide etc.Then, the polymerization by forming any key such as acid amides, acid imide, ester, ether and thioether each other of described monomer is so that synthesize photosensitive polymers used among the present invention.In addition for example, can at first synthesize main chain, introduce the light sensitivity side chain then thereon, thereby make photosensitive polymer used among the present invention as polymer such as polyimides, poly-(sulphur) ether, paracyanogen urate, polyamide-imides, polyethers.
Adopt photosensitive polymers such as paracyanogen urate, polyamide-imides, polyester and poly-(sulphur) ether of method for preparing to wait the method for preparing the flexible metal clad laminate film among the present invention as described below.
Prepared photosensitive polymers is dissolved in makes photosensitive polymers solution in the solvent.The fusing point of described solvent is 30～400 ℃, viscosity 0.5～1000cps (centipoise).Can use the mixture of a kind of solvent or at least two kinds of solvents.Such as preferred N-methyl pyrrolidone (NMP) or N, N-dimethylacetylamide (DMAC).In addition, the concentration of prepared photosensitive polymers solution is preferably 0.5～60 weight %, and viscosity is preferably 10～1, and 000,000cps.
The photosensitive polymers solution for preparing is coated on the metallic films such as copper, platinum, gold, silver and aluminium, thus the coating of obtaining.Remove solvent in the coating by means such as heating, decompression or air blast then.
Then, remove the coating surface of solvent, thereby form flexible insulating film with the ultraviolet ray irradiation.The result can obtain flexible metal clad laminate film.The light source of Shi Yonging can be linearly polarized photon, partial poolarized light or non-polarized light herein, can be oblique fire to the irradiation of coating surface, also can be vertical irradiation.
If adopt photo-sensistive polyimide, because its dissolubility in solvent is less, so generally use light-sensitive polyamic as precursor.Therefore also must carry out forming the imidizate operation of polyimides from polyamic acid.
Adopt the method for polyimides acid solution production flexible metal clad laminate film as described below.
At first prepare light-sensitive polyamic solution, it is coated on the metallic film to form coating as the precursor of photo-sensistive polyimide.After removing the solvent in the coating,, form photo-sensistive polyimide with the polyimide acid imidizate in the not solvent-laden coating.Before or after imidizate, the irradiation coating surface makes photo-sensistive polyimide crosslinked and form flexible insulating film.Thereby obtained flexible metal clad laminate film by above step.Except the imidizate operation that adds, all methods and condition be consistent with above-mentioned other photosensitive polymers almost.
Among the present invention, the imidizate operation is preferably carried out after the crosslinking with radiation operation because can reduce like this occurred when flexible metal clad laminate film at high temperature carries out the imidizate operation as problems such as dimensional stabilitys.
Below will introduce the present invention preparation method on the other hand in detail.That is to say that this method relates to the flexible metal clad laminate film that has adhesive between metallic film and flexible insulating film.
At first, prepare photosensitive polymers, then this photosensitive polymers is dissolved in and obtains photosensitive polymers solution in the solvent with aforementioned identical method and condition.It is on glass such as (but being not limited to) that this photosensitive polymers solution is coated in substrate, forms coating.Remove solvent in the coating with aforementioned same mode and condition then, shine not solvent-laden coating, by the flexible insulating film that is cross-linked to form of photosensitive polymers in the coating.
When adopting photo-sensistive polyimide, it is on glass as (but being not limited to) that aforementioned light sensitivity polyamic acid solution is coated in substrate, forms coating.Remove solvent in the coating with aforementioned same mode and condition then, with the light-sensitive polyamic imidizate to form photo-sensistive polyimide.Before or after the imidizate operation, shine not solvent-laden coating, by the flexible insulating film that is cross-linked to form of photo-sensistive polyimide in the coating.In view of with aforementioned same reason, preferably after crosslinked operation, carry out the imidizate operation.
The flexible insulating film that forms is peeled off from substrate, and flexible insulating film and metallic film under will peeling off with adhesive are bonded together.So just obtained also comprising the flexible metal clad laminate film of adhesive phase.
As previously mentioned, owing to comprise the flexible insulating film of photocrosslinkable polymer resin in the flexible metal clad laminate film for preparing among the present invention, so the raising of the dimensional stability of product, warpage and distortion reduce, and physical property is good.
Embodiment
Describe the present invention in detail hereinafter with reference to embodiment and Comparative Examples.But should be appreciated that these embodiment only are used for describing the present invention, and the present invention should be interpreted as only be confined to these embodiment.
Preparation example 1: the preparation of light sensitivity paracyanogen urate
Preparation example 1-1: the light sensitivity paracyanogen urate of band cinnamate side chain
(1) triazine monomers is synthetic
In being filled with the three-neck flask of nitrogen, 10 gram 4-(2-tetrahydro-pyran oxy) bromobenzenes are dissolved in 50 milliliters of anhydrous tetrahydro furans, reaction is 24 hours in the presence of magnesium.This solution slowly is added drop-wise in the another kind of solution ,-20 ℃, be filled with in the three-neck flask of nitrogen reaction 12 hours, a kind of solution in back is 7.17 grams 2,4,6-three chloro-1,3, the 5-s-triazine is dissolved in 200 milliliters of anhydrous tetrahydro furans.After the reaction, at room temperature make the reaction solution decompression, slough oxolane, be dissolved in the ethyl acetate then.Described solution with after alkali lye mixes, is acutely rocked with extracting impurities, isolate water and remove from solution, at room temperature ethyl acetate is removed in decompression then.Except that being recrystallized, the residual solid matter in back that desolvates obtains 8.2 gram triazine monomers in n-hexane.
(2) polymerization of paracyanogen urate
3.77 gram bisphenol-As, 1.23 gram NaOH and 0.59 are restrained hexadecyldimethyl benzyl ammonium benzyl chloride leach in 100 ml distilled waters.This solution is moved in single neck flask, be equipped with in this flask that 5.13 gram triazine monomers that (1) by preparation example 1-1 make are dissolved in 50 milliliters of chloroforms and the solution that obtains.Then mixed solution was stirred 12 hours.After the reaction, the solution that obtains is slowly splashed into formation precipitation, filtration under diminished pressure precipitation separation then in the methyl alcohol.The solid matter that obtains 40 ℃ of following vacuum drying, is made 4.4 gram paracyanogen urates.
(3) reformation of paracyanogen urate
The paracyanogen urate that 3.5 grams are obtained by (2) of preparation example 1-1 is dissolved in 40 milliliters of oxolanes and the 15 milliliters of ethanol.In above-mentioned solution, add 0.18 gram p-methyl benzenesulfonic acid pyridiniujm, at room temperature reacted 24 hours.After the reaction, reaction solution slowly is added drop-wise to formation precipitation in the methyl alcohol, filters and precipitation separation.Should precipitate 40 ℃ of following vacuum drying, obtain the paracyanogen urate of 2.1 gram hydroxyls.
(4) introducing of cinnamate light sensitivity group
The paracyanogen urates of 3 gram hydroxyls are dissolved in 25 milliliters of oxolanes and the 5.57 milliliters of triethylamines.7.16 gram cinnamoyl chlorides are dissolved in 5 milliliters of oxolanes and obtain solution, this solution is added drop-wise under 0 ℃ in the above-mentioned paracyanogen urate solution then, reacted 2 hours.After the reaction, the solution that reaction is obtained slowly is added drop-wise to and forms polymer in the methyl alcohol, filters, separates this polymer then.Repeat this step twice.The gained sediment obtains the paracyanogen urate of 3.2 gram band cinnamic acid ester group light sensitivity side chains 40 ℃ of following vacuum drying.
Preparation example 1-2: the light sensitivity paracyanogen urate of band chalcone group side chain
(1) chalcone light sensitivity group is synthetic
10 gram 4-methoxyl group chalcones and 2.05 gram Cymags are dissolved in 100 milliliters of dimethyl sulfoxide (DMSO)s, reacted then 24 hours.After reaction finished, the solution that reaction is obtained mixed with chloroform, and later and distilled water stirs, with extracting impurities.Remove aqueous solution mutually after, this solution at room temperature reduced pressure removes chloroform.After remaining solid phase is recrystallized,, obtain the 4-hydroxyl chalcone that 5.4 grams are used for light reaction 40 ℃ of following vacuum drying in methyl alcohol.
(2) introducing of chalcone functional group
The paracyanogen urate that 5 gram 4-hydroxyl chalcones and 6.14 are restrained by preparation example 1-1 (3) synthetic hydroxyl is dissolved in 60 milliliters of oxolanes.0.38 gram azo dicarbonic acid diethyl ester and 0.58 gram triphenylphosphine are joined in the above-mentioned solution, at room temperature reacted 24 hours.After the reaction, the solution that reaction is obtained slowly is added drop-wise in the methyl alcohol, forms polymer, this polymer of filtration under diminished pressure then.Repeat this step twice.This is deposited in 40 ℃ of following vacuum drying, obtains the paracyanogen urate of 5.7 gram band chalcone light sensitivity side chains.
Preparation example 1-3: the light sensitivity paracyanogen urate of band cumarin side chain
(1) introducing of cumarin light sensitivity group
3.57 gram umbelliferone and 6.14 grams are dissolved in 60 milliliters of oxolanes by the paracyanogen urate of preparation example 1-1 (3) synthetic hydroxyl.0.38 gram azo dicarbonic acid diethyl ester and 0.58 gram triphenylphosphine are joined in the above-mentioned solution, at room temperature reacted 24 hours.After the reaction, the solution that reaction is obtained slowly is added drop-wise in the methyl alcohol, forms polymer, this polymer of filtration under diminished pressure then.Repeat this step twice.This is deposited in 40 ℃ of following vacuum drying, obtains the paracyanogen urate of 5.3 gram band cumarin base light sensitivity side chains.
Preparation example 2: light sensitivity polyester synthetic
Preparation example 2-1: the light sensitivity polyester of band cinnamate base side chain
(1) introducing of alcohol functional group
90 gram 4-(2-tetrahydro-pyran oxy) bromobenzenes are inserted in the three-neck flask that is filled with nitrogen, then with 500 milliliters of anhydrous tetrahydro furans dissolvings, and with 9.6 restrain reactive magnesiums 3 hours.This drips of solution is added in oxolane (200 milliliters) solution of cyanuric chloride (18.4 gram), this mixture of vigorous stirring, reaction is 6 hours under reflux temperature.
After reaction is finished, 3 gram p-methyl benzenesulfonic acid pyridiniujms are joined in this solution, continue reaction 6 hours.After the reaction, the solution that reaction is obtained is removed oxolane through decompression distillation, then the solution that obtains is dissolved in the carrene, and after the filter of filling with silica gel filtered, decompression distillation removed and desolvates.
Be in 1: 1 the mixed solvent behind the recrystallization at the ratio of carrene and n-hexane at last, this solution of filtration under diminished pressure.30.1 grams 2,4,6-trihydroxy phenyl-1,3,5-triazines will be obtained after the solid formation vacuum drying that obtain.
(2) contain diol monomer synthetic of cinnamoyl group
14.8 gram cinnamic acids are inserted in the round-bottomed flask.Add 17.8 gram thionyl chloride (SOCl therein 2), stir this mixture.And then in this flask, add 0.5ml dimethyl formamide (DMF), this mixture was at room temperature reacted 24 hours.React the back decompression distillation, obtained 16 gram cinnamoyl chlorides.
With 35.7 grams by (1) of preparation example 2-1 obtain 2,4,6-trihydroxy phenyl-1,3,5-triazines is inserted in the round-bottomed flask, and is dissolved in 400 milliliters of chloroforms.In this solution, add 15.2 gram triethylamines, temperature with solution is reduced to-5 ℃ then, this solution of strong agitation also reacted 12 hours, slowly dripped cinnamoyl chloride solution simultaneously, and described cinnamoyl chloride solution is the dilute solution that 20 milliliters of anhydrous tetrahydro furans is added 16 gram cinnamoyl chlorides.
After reaction was finished, the solution decompression that reaction is obtained distilled to remove oxolane, and with after the carrene dissolving, the filter of filling with silica gel filters then, and filtration under diminished pressure removes and desolvates then.
In being 1: 1 mixed solvent, the ratio of carrene and n-hexane is recrystallized filtration under diminished pressure solution at last.With the solid formation vacuum drying that obtains, obtain the diol monomer that 36.7 grams contain the cinnamoyl group.
(3) polymerization of the polyester of band cinnamate functional group
48.7 grams are inserted in the round-bottomed flask that is filled with nitrogen by the triazine monomers that (2) of preparation example 2-1 obtain, dissolve with 400 milliliters of oxolanes then.In this solution, add 20.238 gram triethylamines.
After being dissolved in 20.3 gram terephthalyl chlorides in 100 milliliters of anhydrous tetrahydro furans, this solution of vigorous stirring when this solution slowly being splashed in the solution that is dissolved with above-mentioned triazine monomers and triethylamine, makes this solution reaction 12 hours.After having reacted, the solution that reaction obtains is slowly poured in the methyl alcohol, obtained precipitation.With sedimentation and filtration final vacuum drying.The sediment that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, repeat this process and repeat twice, vacuum drying then obtains finally that 37.1g utilizes triazine ring and polyester with cinnamate functional group.
Preparation example 2-2: the light sensitivity polyester of band chalcone group side chain
(1) chalcone light sensitivity group is synthetic
10 gram 4-methoxyl group chalcones and 2.05 gram Cymags are dissolved in 100 milliliters of dimethyl sulfoxide (DMSO)s, react 24 hours.After reaction finished, the solution that reaction is obtained mixed with chloroform, stirs with distilled water then, with extracting impurities.Remove aqueous solution mutually after, this solution is at room temperature reduced pressure, to remove chloroform.After the solid formation of remnants was recrystallized in methyl alcohol, this solid of vacuum drying obtained the 4-hydroxyl chalcone that 20.1 grams are used for light reaction.
(2) introducing of chalcone functional group in the triazine ring
To insert in the round-bottomed flask that is filled with nitrogen according to 23.8 synthetic gram 4-hydroxyl chalcones of preparation example 2-2 (1), it will be dissolved in 240 milliliters of anhydrous tetrahydro furans then.2.4 gram sodium hydrides (NaH) are joined in the above-mentioned solution, at room temperature reacted 6 hours.Under-5 ℃, this solution was slowly added in the another kind of solution reaction 24 hours under vigorous stirring, described back one solution is that 18.4 gram cyanuric chlorides are packed in the round-bottomed flask, then it is dissolved in 200 milliliters of anhydrous tetrahydro furans and forms.After reaction was finished, oxolane was removed in decompression distillation, then residual solid is dissolved in the chloroform again.This solution is washed three times with distilled water in separatory funnel,, dehumidify with calcium chloride then with extracting impurities.Then chloroform is removed in this solution decompression distillation, the mixed solvent with carrene and n-hexane is recrystallized again.With the recrystallization thing filtration under diminished pressure final vacuum drying that obtains, obtain the pyrrolotriazine derivatives of 30.2 gram band chalcone functional groups.
(3) triazine monomers of band functionalized with glycols group is synthetic
In nitrogen, 51.4 gram 4-(2-tetrahydro-pyran oxy) bromobenzenes are dissolved in 300 milliliters of anhydrous tetrahydro furans,, obtain grignard reagent solution with 7.2 gram reactive magnesiums 3 hours.To be dissolved in 300 milliliters of anhydrous tetrahydro furans by pyrrolotriazine derivatives 38.6 grams of preparation example 2-2 (2) synthetic band chalcone light sensitivity group, this solution slowly is added drop-wise in the above-mentioned grignard reagent solution, at room temperature reacted 12 hours.After the reaction, in this solution, add 3 gram p-methyl benzenesulfonic acid pyridiniujms, continue reaction 6 hours.After the reaction, oxolane is removed in the solution decompression distillation that reaction obtains, then this solution is dissolved with carrene, after filtering with the filter that is filled with silica gel, decompression distillation removes and desolvates.
At last, in the ratio of carrene and n-hexane is 1: 1 mixed solvent, be recrystallized, this solution decompression is filtered.Obtain the triazine monomers of 42.3 gram band functionalized with glycols groups after the solid formation vacuum drying that obtains.
(4) polymerization of the polyester of band chalcone functional group
To insert in the round-bottomed flask that is filled with nitrogen by preparation example 2-2 (3) synthetic triazine monomers 50.1 grams, with 500 milliliters of anhydrous tetrahydro furan dissolvings.In this solution, add 20.2 gram triethylamines.20.3 gram terephthalyl chlorides are dissolved in 100 milliliters of anhydrous tetrahydro furans, then it slowly are added drop-wise in the above-mentioned solution that is dissolved with triazine monomers and triethylamine this solution reaction of vigorous stirring 12 hours.After the reaction, the solution that reaction is obtained is slowly poured in the methyl alcohol and is precipitated, and filters and vacuum drying.The polymer that obtains is dissolved in the oxolane again, in methyl alcohol, precipitates then, repeat this step twice final vacuum drying, obtain the light sensitivity polyester of 42.1 gram band chalcone functional groups at last.
Preparation example 2-3: the light sensitivity polyester of band cumarin group side chain
(1) introducing of cumarin light sensitivity group
16.2 gram umbelliferones and 2.4 sodium hydrides (NaH) are inserted in the round-bottomed flask that is filled with nitrogen, it is dissolved in 160 milliliters of anhydrous tetrahydro furans then.Subsequently this solution of vigorous stirring and make its reaction 6 hours.Then this solution is slowly splashed in the another kind of solution ,-5 ℃ of following vigorous stirring reactions 24 hours, the preparation method of described another kind of solution was that adding 18.4 gram cyanuric chlorides are dissolved in it in 200 milliliters of anhydrous tetrahydro furans then in round bottom burns.After the reaction, oxolane is removed in decompression distillation, then remaining solid formation is dissolved in the chloroform again.This solution is washed three times with extracting impurities with distilled water in separatory funnel, dehumidify with calcium chloride then.Chloroform is removed in this solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.With the recrystallization thing filtration under diminished pressure final vacuum drying that obtains, obtain the pyrrolotriazine derivatives of 28.7 gram band cumarin functional groups.
(2) have triazine monomers synthetic of two amine functional groups
In nitrogen, 51.4 gram 4-(2-tetrahydro-pyran oxy) bromobenzenes are dissolved in 300 milliliters of anhydrous tetrahydro furans, with 7.2 gram reactive magnesiums 6 hours, obtain grignard reagent solution.To be dissolved in 300 milliliters of anhydrous tetrahydro furans by triazine 31.1 grams of preparation example 2-3 (1) synthetic band cumarin light sensitivity group, this solution slowly is added drop-wise in the grignard reagent solution, at room temperature reacted 12 hours.After the reaction, in this solution, add 3 gram p-methyl benzenesulfonic acid pyridiniujms, continue reaction 6 hours.After the reaction, oxolane is removed in the solution decompression distillation that reaction obtains, then the gained solid is dissolved in the carrene, after filtering with the filter that is filled with silica gel, decompression distillation removes and desolvates.
At last, in being 1: 1 mixed solvent, the ratio of carrene and n-hexane is recrystallized, then this solution of filtration under diminished pressure.The triazine monomers of 35.7 gram band functionalized with glycols groups will be obtained after the solid formation vacuum drying that obtain.
(3) band cumarin functional group polyester is synthetic
To insert in the round-bottomed flask that is filled with nitrogen by preparation example 2-3 (2) synthetic triazine monomers 45.5 grams, and dissolve with 500 milliliters of anhydrous tetrahydro furans.In this solution, add 20.2 gram triethylamines.20.3 gram terephthalyl chlorides are dissolved in 100 milliliters of anhydrous tetrahydro furans, then it slowly are added drop-wise in the above-mentioned solution that is dissolved with triazine monomers and triethylamine, this solution of vigorous stirring makes its reaction 12 hours.After the reaction, the solution that reaction is obtained is slowly poured in the methyl alcohol and is precipitated, and filters vacuum drying.The polymer that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, repeat this step twice, vacuum drying then obtains the polyester that 35.6 grams are with cumarin functional groups at last.
Preparation example 3: light sensitivity polyethers synthetic
Preparation example 3-1: the light sensitivity polyethers of band cinnamate group side chain
(1) reformation of triazine ring
25.7 gram 4-(2-tetrahydro-pyran oxy) bromobenzenes are dissolved in being filled with the three-neck flask of nitrogen in 250 milliliters of anhydrous tetrahydro furans, added 3 gram reactive magnesiums then 24 hours.In being filled with the three-neck flask of nitrogen, this solution slowly is added drop-wise under-20 ℃ by 18.4 gram cyanuric chlorides is dissolved in the 200ml anhydrous tetrahydro furan and in the solution that forms, reacted 12 hours.
After the reaction, reaction solution at room temperature reduced pressure remove oxolane, be dissolved in the ethyl acetate then.With after alkali lye mixes, vigorous stirring is separated with the water layering and with this solution with extracting impurities, this solution is at room temperature reduced pressure remove ethyl acetate then with this solution.
The remaining solid formation that removes after desolvating is recrystallized in n-hexane, obtains 30 gram 2-(4-(2-tetrahydro-pyran oxy) phenyl)-4,6-two chloro-1,3,5-triazines.
(2) introducing of hydroxy functional group on the triazine ring
Material 32.6 grams that will be obtained by (1) of preparation example 3-1 are inserted in the round-bottomed flask, and it is dissolved in 300 milliliters of oxolanes, add 0.3 gram p-methyl benzenesulfonic acid pyridiniujm and 50 milliliters of ethanol then, react 24 hours.
After having reacted, decompression distillation removes and desolvates, and the residual solid that obtains is dissolved in the carrene again, mixes twice of extracting impurities then in separatory funnel with distilled water.In carrene, add calcium chloride to remove moisture.Then with this solution once more decompression distillation remove and to desolvate.This solid formation is recrystallized in the mixed solvent of carrene and n-hexane, obtains 20 gram 2-(4-hydroxyphenyl)-4,6-two chloro-1,3,5-triazines.
(3) triazine ring of band cinnamate side chain is synthetic
Pyrrolotriazine derivatives 24.2 grams that will be prepared by (2) of preparation example 3-1 are inserted in the round-bottomed flask that is filled with nitrogen, it are dissolved in 200 milliliters of anhydrous tetrahydro furans then.After in this solution, adding 15.2 gram triethylamines, the temperature of solution is reduced to-5 ℃, under vigorous stirring, slowly drips cinnamoyl chloride solution, reacted 12 hours, this cinnamoyl chloride solution is to add the solution that 100 milliliters of anhydrous tetrahydro furan dilutions obtain in 25 gram cinnamoyl chlorides.
After the reaction, oxolane is removed in the solution decompression distillation that reaction obtains, then residual solid is dissolved in the carrene, after filtering with the filter that is filled with silica gel, decompression distillation removes and desolvates.
At last, in being 1: 1 mixed solvent, the ratio of carrene and n-hexane is recrystallized, then this solution of filtration under diminished pressure.Obtain the pyrrolotriazine derivatives of 31 gram band cinnamate side chains after the solid formation vacuum drying that obtains.
(4) triazine monomers of band dihalo-functional group is synthetic
To insert in the round-bottomed flask by preparation example 3-1 (3) synthetic pyrrolotriazine derivatives 37.2 grams, and be dissolved in 400 milliliters of chloroforms.25.6 gram 4-chlorophenols and 8g dissolution of sodium hydroxide in 300 milliliters of distilled water that are dissolved with 3 gram softex kws, are mixed it vigorous reaction 24 hours then with above-mentioned pyrrolotriazine derivatives solution.After the reaction, organic solution is separated out, the solution that reaction is obtained moves in the separatory funnel, washs three times with extracting impurities with distilled water, removes moisture with calcium chloride then.Should water-free solution decompression distillation remove chloroform, in the mixed solvent of carrene and n-hexane, be recrystallized then.
To precipitate crystal filtration under diminished pressure final vacuum drying, obtain 50.5 gram triazine monomers.
(5) polymerization of the polyethers of band cinnamate functional group
Triazine monomers 55.3 grams that will be obtained by (4) of preparation example 3-1 are inserted in the round-bottomed flask that is filled with nitrogen, and are dissolved in 600 milliliters of nitrobenzene.The solution that 11 gram hydroquinones, 8 gram NaOH and 0.3 gram softex kw are dissolved in 100 ml waters mixes with the nitrobenzene solution that is dissolved with above-mentioned triazine monomers, and vigorous stirring was reacted 24 hours.After the reaction, the solution that reaction is obtained is slowly poured into and is obtained precipitation in the methyl alcohol, filters this post precipitation vacuum drying.The polymer that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, this step repeats twice, and then vacuum drying obtains the polyethers that 35.9 grams are with cinnamate functional groups at last.
Preparation example 3-2: the light sensitivity polyether polymer of band chalcone group side chain
(1) chalcone light sensitivity group is synthetic
10 gram 4-methoxyl group chalcones and 2.05 gram Cymags are dissolved in 100 milliliters of dimethyl sulfoxide (DMSO)s, reacted 24 hours.After the reaction, the solution that reaction is obtained stirs with the chloroform mixing and with distilled water, with extracting impurities.After removing water-soluble liquid phase, this solution at room temperature reduced pressure remove chloroform.After the solid formation of remnants is recrystallized,, obtain the 4-hydroxyl chalcone that 23 grams are used for light reaction at 40 ℃ of following vacuum drying solids in methyl alcohol.
(2) introducing of chalcone functional group on the triazine ring
To insert in the round-bottomed flask that is filled with nitrogen by preparation example 3-2 (1) synthetic 4-hydroxyl chalcone 23.8 grams, and be dissolved in 240 milliliters of anhydrous tetrahydro furans.In this solution, add 2.4 gram sodium hydrides (NaH), at room temperature reacted 6 hours.Solution slowly is added drop-wise under-5 ℃ in the cyanuric chloride solution, vigorous stirring, and reaction is 24 hours in round-bottomed flask, and this cyanuric chloride solution is to make 18.4 gram cyanuric chlorides be dissolved in the solution that obtains in 200 milliliters of anhydrous tetrahydro furans.After the reaction, oxolane is removed in decompression distillation, then residual solid is dissolved in the chloroform again.This solution with distilled water washing three times, with extracting impurities, is removed moisture with calcium chloride then in separatory funnel.Then chloroform is removed in this solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized again.The material filtration under diminished pressure final vacuum drying that will be recrystallized obtains the pyrrolotriazine derivatives of 20 gram band chalcone functional groups.
(3) triazine monomers of band dihalo-functional group is synthetic
Pyrrolotriazine derivatives 38.6 grams of the band chalcone functional group that will be obtained by (2) of preparation example 3-2 are inserted in the round-bottomed flask, and are dissolved in 400 milliliters of chloroforms.25.6 gram 4-chlorophenols and 8g dissolution of sodium hydroxide in 300 milliliters of distilled water that are dissolved with 3 gram softex kws, are mixed it vigorous reaction 24 hours then with above-mentioned pyrrolotriazine derivatives solution.After having reacted, organic solution is separated out, the solution that reaction obtains moves in the separatory funnel, washs three times with extracting impurities with distilled water, and removes moisture with calcium chloride.Chloroform is removed in this anhydrous solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.
With the crystal filtration under diminished pressure final vacuum drying that is settled out, obtain 50 gram triazine monomers.
(4) polymerization of band chalcone functional group polyethers
Triazine monomers 56.7 grams that will be obtained by (3) of preparation example 3-2 are inserted in the round-bottomed flask that is filled with nitrogen, and are dissolved in 600 milliliters of nitrobenzene.The solution that 11 gram hydroquinones, 8 gram NaOH and 0.3 gram softex kw are dissolved in 100 ml waters mixes with the nitrobenzene solution that is dissolved with above-mentioned triazine monomers, and vigorous stirring was reacted 24 hours.After the reaction, the solution that reaction is obtained is slowly poured into and is obtained precipitation in the methyl alcohol, filters the final vacuum drying.The polymer that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, this step repeats twice, and then vacuum drying obtains the polyethers that 37.2 grams are with chalcone functional groups at last.
Preparation example 3-3: the light sensitivity polyether polymer of band cumarin group side chain
(1) introducing of cumarin light sensitivity group
16.2 gram umbelliferones and 2.4 sodium hydrides (NaH) are inserted in the round-bottomed flask that is filled with nitrogen, it is dissolved in 160 milliliters of anhydrous tetrahydro furans then.Vigorous stirring was reacted 6 hours subsequently.Slowly splash under vigorous stirring in the cyanuric chloride solution at-5 ℃ then, reacted 24 hours, the preparation method of described cyanuric chloride solution is in round-bottomed flask 18.4 gram cyanuric chlorides to be dissolved in 200 milliliters of oxolanes.After reaction was finished, oxolane was removed in decompression distillation, then residual solid is dissolved in the chloroform again.In separatory funnel, wash this solution three times with extracting impurities with distilled water, and dehumidify with calcium chloride.Then chloroform is removed in this solution decompression distillation, the back is recrystallized in the mixed solution of carrene and n-hexane.The thing filtration under diminished pressure final vacuum drying that will be recrystallized obtains the pyrrolotriazine derivatives of 22 gram band cumarin functional groups.
(2) triazine monomers of band dihalo-functional group is synthetic
Pyrrolotriazine derivatives 31.1 grams of the band cumarin photosensitive group that will be obtained by (1) of preparation example 3-3 are inserted in the round-bottomed flask, and are dissolved in 400 milliliters of chloroforms.25.6 gram 4-chlorophenols and 8g dissolution of sodium hydroxide in 300 milliliters of distilled water that are dissolved with 3 gram softex kws, are mixed it vigorous reaction 24 hours then with above-mentioned pyrrolotriazine derivatives solution.After having reacted, organic solution is separated out, the solution that reaction is obtained moves in the separatory funnel, washs three times with extracting impurities with distilled water, and removes moisture with calcium chloride.Chloroform is removed in this anhydrous solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.
With the crystal filtration under diminished pressure final vacuum drying that is settled out, obtain 45 gram triazine monomers.
(3) polymerization of band cumarin functional group polyethers
Triazine monomers 49.1 grams that will be obtained by (2) of preparation example 3-3 are inserted in the round-bottomed flask that is filled with nitrogen, and are dissolved in 600 milliliters of nitrobenzene.The solution that 11 gram hydroquinones, 8 gram NaOH and 0.3 gram softex kw are dissolved in 100 ml waters mixes with the nitrobenzene solution that is dissolved with above-mentioned triazine monomers, and vigorous stirring was reacted 24 hours.After the reaction, the solution that reaction is obtained is slowly poured into and is obtained precipitation in the methyl alcohol, filters the final vacuum drying.The polymer that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, this step repeats twice, and then vacuum drying obtains the polyethers that 32.3 grams are with cumarin functional groups at last.
Preparation example 4: light sensitivity polythiaether synthetic
Preparation example 4-1: the light sensitivity polythiaether of band cinnamate group side chain
(1) reformation of triazine ring
In being filled with the three-neck flask of nitrogen, 25.7 gram 4-(2-tetrahydro-pyran oxy) bromobenzenes are dissolved in 250 milliliters of anhydrous tetrahydro furans, restrain reactive magnesiums 24 hours with 3 then.In being filled with the three-neck flask of nitrogen, this solution slowly is added drop-wise under-20 ℃ by 18.4 gram cyanuric chlorides is dissolved in 200 milliliters of anhydrous tetrahydro furans and in the solution that forms, reacted 12 hours.
After the reaction, the solution that obtains is dissolved in the ethyl acetate after at room temperature reducing pressure and removing oxolane.With after alkali lye mixes, vigorous stirring is with extracting impurities with this solution, and water phase separated is also removed from this solution, and at room temperature ethyl acetate is removed in decompression then.
Remove the remaining solid formation in back that desolvates and in n-hexane, be recrystallized, obtain 30.1 gram 2-(4-(2-tetrahydro-pyran oxy) phenyl)-4,6-two chloro-1,3,5-triazines.
(2) introducing of hydroxy functional group on the triazine ring
Material 32.6 grams that will be obtained by (1) of preparation example 4-1 are inserted in the round-bottomed flask, and it is dissolved in 300 milliliters of oxolanes, add 0.3 gram p-methyl benzenesulfonic acid pyridiniujm and 50 milliliters of ethanol then, react 24 hours.
After having reacted, decompression distillation removes and desolvates, and then the residual solid thing is dissolved in the carrene again, mixes with distilled water in separatory funnel then, with extracting impurities.In dichloromethane solution, place calcium chloride to remove moisture, then with this solution once more decompression distillation remove and desolvate.This solid formation is recrystallized in the mixed solvent of carrene and n-hexane, obtains 20.5 gram 2-(4-tetrahydro-pyran oxy)-4,6-two chloro-1,3,5-triazines.
(3) triazine ring of band cinnamate side chain is synthetic
Pyrrolotriazine derivatives 24.2 grams that will be obtained by (2) of preparation example 4-1 are inserted in the round-bottomed flask that is filled with nitrogen, it are dissolved in 200 milliliters of anhydrous tetrahydro furans then.After in this solution, adding 15.2 gram triethylamines and the temperature of solution being reduced to-5 ℃, slowly drip cinnamoyl chloride solution on one side, vigorous stirring was reacted 12 hours on one side, and described cinnamoyl chloride solution is obtained by 100 milliliters of anhydrous tetrahydro furan dilution 25 gram cinnamoyl chlorides.
After the reaction, oxolane is removed in the solution decompression distillation that reaction obtains, then remaining solid formation is dissolved in the carrene, after filtering with the filter that is filled with silica gel, decompression distillation removes and desolvates.
At last, in the ratio of carrene and n-hexane is 1: 1 mixed solvent, be recrystallized, then this solution decompression filtered.The pyrrolotriazine derivatives of 30.2 gram band cinnamate side chains will be obtained after the solid formation vacuum drying that obtain.
(4) triazine monomers of band dihalo-functional group is synthetic
Pyrrolotriazine derivatives 37.2 grams that will be obtained by (3) of preparation example 4-1 are inserted in the round-bottomed flask, and are dissolved in 400 milliliters of chloroforms.25.6 gram 4-chlorophenols and 8g dissolution of sodium hydroxide in 300 milliliters of distilled water that are dissolved with 3 gram softex kws, are mixed vigorous reaction 24 hours then with above-mentioned triazine solution.After having reacted, organic solution is separated out, the solution that reaction is obtained moves in the separatory funnel, with distilled water washing three times, with extracting impurities, removes moisture with calcium chloride then.Chloroform is removed in this anhydrous solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.
With the crystal filtration under diminished pressure final vacuum drying of separating out, obtain 50.3 gram triazine monomers.
(5) polymerization of the polythiaether of band cinnamate functional group
Triazine monomers 55.3 grams that will be obtained by (4) of preparation example 4-1 are inserted in the round-bottomed flask that is filled with nitrogen, and are dissolved in 600 milliliters of nitrobenzene.With 14.2 grams 1, the solution that 4-dimercaptobenzene, 8 gram NaOH and 0.3 gram softex kw are dissolved in 100 ml waters mixes with the nitrobenzene solution that is dissolved with above-mentioned triazine monomers, and vigorous stirring was reacted 24 hours.After the reaction, the solution that reaction is obtained is slowly poured into and is obtained precipitation in the methyl alcohol, filters the final vacuum drying.The polymer that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, this step repeats twice, and then vacuum drying obtains the polythiaether that 35.9 grams are with cinnamate functional groups at last.
Preparation example 4-2: the light sensitivity polythiaether of band chalcone group side chain
(1) chalcone light sensitivity group is synthetic
10 gram 4-methoxyl group chalcones and 2.05 gram Cymags are dissolved in 100 milliliters of dimethyl sulfoxide (DMSO)s, reacted 24 hours.After the reaction, the solution that reaction is obtained mixes with chloroform, stirs with distilled water then, with extracting impurities.After removing water-soluble liquid phase, this solution at room temperature reduced pressure remove chloroform.After the solid formation of remnants is recrystallized, solid 40 ℃ of following vacuum drying, is obtained the 4-hydroxyl chalcone that 20.7 grams are used for light reaction in methyl alcohol.
(2) introducing of chalcone functional group on the triazine ring
To insert in the round-bottomed flask that is filled with nitrogen by preparation example 4-2 (1) synthetic 4-hydroxyl chalcone 23.8 grams, and be dissolved in 240 milliliters of anhydrous tetrahydro furans.In this solution, add 2.4 gram sodium hydrides (NaH), at room temperature reacted 6 hours.Under the vigorous stirring, this solution slowly is added drop-wise under-5 ℃ in the cyanuric chloride solution, reacted 24 hours, the preparation method of described cyanuric chloride solution is, in round-bottomed flask, add 18.4 gram cyanuric chlorides, it is dissolved in 200 milliliters of anhydrous tetrahydro furans then.After the reaction, oxolane is removed in the solution decompression distillation that reaction obtains, then residual solid is dissolved in the chloroform again.With this solution in separatory funnel with distilled water washing three times, with extracting impurities, and remove moisture with calcium chloride.Then chloroform is removed in this solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.The thing filtration under diminished pressure final vacuum drying that will be recrystallized obtains the pyrrolotriazine derivatives of 31.6 gram band chalcone functional groups.
(3) triazine monomers of band dihalo-functional group is synthetic
Pyrrolotriazine derivatives 38.6 grams that will be obtained by (2) of preparation example 4-2 are inserted in the round-bottomed flask, and are dissolved in 400 milliliters of chloroforms.25.6 gram 4-chlorophenols and 8g dissolution of sodium hydroxide in 300 milliliters of distilled water that are dissolved with 3 gram softex kws, are mixed it vigorous reaction 24 hours then with above-mentioned triazine solution.After having reacted, organic solution is separated out, the solution that reaction is obtained moves in the separatory funnel, with distilled water washing three times, with extracting impurities, and removes moisture with calcium chloride.Chloroform is removed in this anhydrous solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.
With the crystal filtration under diminished pressure final vacuum drying of separating out, obtain 50.2 gram triazine monomers.
(4) polymerization of the polythiaether of band chalcone functional group
Triazine monomers 56.7 grams that will be obtained by (3) of preparation example 4-2 are inserted in the round-bottomed flask that is filled with nitrogen, and are dissolved in 600 milliliters of nitrobenzene.The solution that 14.2 gram dimercaptobenzenes, 8 gram NaOH and 0.3 gram softex kw are dissolved in 100 ml waters mixes with the nitrobenzene solution that is dissolved with above-mentioned triazine monomers, and vigorous stirring was reacted 24 hours.After the reaction, the solution that reaction is obtained is slowly poured into and is obtained precipitation, this post precipitation vacuum drying after the filtration in the methyl alcohol.The polymer that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, this step repeats twice, and then vacuum drying obtains the polythiaether that 35.2 grams are with chalcone functional groups at last.
Preparation example 4-3: the light sensitivity polysulfide polymers of band cumarin group side chain
(1) introducing of cumarin light sensitivity group
16.2 gram umbelliferones and 2.4g sodium hydride (NaH) are inserted in the round-bottomed flask that is filled with nitrogen, it is dissolved in 160 milliliters of anhydrous tetrahydro furans then.Vigorous stirring solution reacted 6 hours subsequently.Slowly add cyanuric chloride solution down at-5 ℃ then, vigorous stirring was reacted 24 hours, and the preparation method of described cyanuric chloride solution is that the 18.4 gram cyanuric chlorides of packing in round-bottomed flask are dissolved in it in 200 milliliters of anhydrous tetrahydro furans then.After reaction was finished, oxolane was removed in decompression distillation, then residual solid is dissolved in the chloroform again.In separatory funnel, wash three times with extracting impurities with distilled water, dehumidify with calcium chloride then.In the mixed solution of carrene and n-hexane, be recrystallized after the distillation of this solution decompression removed chloroform.The recrystallization thing filtration under diminished pressure final vacuum drying that obtains obtains the pyrrolotriazine derivatives that 29.7 grams are with cumarin functional groups.
(2) triazine monomers of band dihalo-functional group is synthetic
Pyrrolotriazine derivatives 31.1 grams that will be obtained having cumarin light sensitivity functional group by (1) of preparation example 4-3 are inserted in the round-bottomed flask, and are dissolved in 400 milliliters of chloroforms.25.6 gram 4-chlorophenols and 8g dissolution of sodium hydroxide are dissolved with in the 3 gram softex kw distilled water at 300 milliliters, mix vigorous reaction 24 hours then with above-mentioned triazine solution.After having reacted, organic solution is separated out, the solution that obtains of reaction moves in the separatory funnel, with distilled water washing three times, extracting impurities, and removes moisture with calcium chloride.Chloroform is removed in the solution decompression distillation of removing moisture, in the mixed solvent of carrene and n-hexane, be recrystallized then.
With the crystal filtration under diminished pressure final vacuum drying of separating out, obtain 40.2 gram triazine monomers.
(3) polymerization of the polythiaether of band cumarin functional group
Triazine monomers 49.1 grams that will be obtained by (2) of preparation example 4-3 are inserted in the round-bottomed flask that is filled with nitrogen, and are dissolved in 600 milliliters of nitrobenzene.With 14.2 grams 1, the solution that 4-dimercaptobenzene, 8 gram NaOH and 0.3 gram softex kw are dissolved in 100 ml waters mixes with the nitrobenzene solution of above-mentioned triazine monomers, and vigorous stirring was reacted 24 hours.After the reaction, the solution that reaction is obtained is slowly poured into and is obtained precipitation in the methyl alcohol, filters the final vacuum drying.The precipitation that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, this step repeats twice, and then vacuum drying obtains the polythiaether that 37 grams are with cumarin functional groups at last.
Preparation example 5: photosensitive polyamide-imido synthetic
Preparation example 5-1: the photosensitive polyamide-acid imide of band cinnamate group side chain
(1) reformation of triazine ring
In being filled with the three-neck flask of nitrogen, 27.1 gram 4-(2-oxinane ylmethoxy) bromobenzenes are dissolved in 250 milliliters of anhydrous tetrahydro furans, restrain reactive magnesiums 24 hours with 3 then.This solution slowly is added drop-wise under-20 ℃ by being that 18.4 gram cyanuric chlorides are dissolved in the solution that 200 milliliters of anhydrous tetrahydro furans obtain, it was reacted 12 hours in being filled with the three-neck flask of nitrogen.
After the reaction, the solution that obtains at room temperature reduced pressure remove oxolane, be dissolved in the ethyl acetate then.Mix with alkali lye then, vigorous stirring is with extracting impurities, makes the water layering and removes from solution, and at room temperature ethyl acetate is removed in decompression then.
The remaining solid formation that removes after desolvating is recrystallized in n-hexane, obtains 30 gram 2-(4-(2-oxinane ylmethoxy) phenyl)-4,6-two chloro-1,3,5-triazines.
(2) introducing of hydroxy functional group on the triazine ring
Material 34.0 grams that will be obtained by (1) of preparation example 5-1 are inserted in the round-bottomed flask, and it is dissolved in 300 milliliters of oxolanes, add 0.3 gram p-methyl benzenesulfonic acid pyridiniujm and 50 milliliters of ethanol then, react 24 hours.
After having reacted, decompression distillation removes and desolvates, and the solid that obtains is dissolved in the carrene again, mixes twice of extracting impurities then in separatory funnel with distilled water.In dichloromethane solution, add calcium chloride to remove moisture, then with this solution once more decompression distillation remove and desolvate.After being recrystallized, the solid formation that obtains obtains 20.6 gram 2-(4-hydroxyphenyl)-4 in the mixed solvent of carrene and n-hexane, 6-two chloro-1,3,5-triazines.
(3) triazine ring of band cinnamate side chain is synthetic
Pyrrolotriazine derivatives 25.6 grams that will be obtained by (2) of preparation example 5-1 are inserted in the round-bottomed flask that is filled with nitrogen, it are dissolved in 200 milliliters of anhydrous tetrahydro furans then.Temperature with solution behind the adding 15.2 gram triethylamines is reduced to-5 ℃, on one side the slow cinnamoyl chloride solution that drips, one side vigorous stirring was reacted 12 hours, and described cinnamoyl chloride solution obtains after restraining cinnamoyl chlorides with 100 milliliters of anhydrous tetrahydro furans dilutions 25.
After the reaction, oxolane is removed in the solution decompression distillation that reaction obtains, then remaining solid formation is dissolved in the carrene, after filtering with the filter that is filled with silica gel, decompression distillation removes and desolvates.
At last, in the mixed solvent of carrene and n-hexane, be recrystallized, then filtration under diminished pressure.Obtain the pyrrolotriazine derivatives of 35.1 gram band cinnamate side chains after the solid formation vacuum drying that obtains.
(4) synthetic with the triazine monomers of two amine functional groups
Pyrrolotriazine derivatives 38.6 grams that will be obtained by (3) of preparation example 5-1 are inserted in the round-bottomed flask, and are dissolved in 400 milliliters of chloroforms.32.8 gram 4-amino phenols and 1 2g dissolution of sodium hydroxide in 300 milliliters of distilled water that are dissolved with 3 gram softex kws, are mixed vigorous reaction 24 hours then with above-mentioned pyrrolotriazine derivatives solution.After having reacted, organic solution is separated out, the solution that obtains of reaction moves in the separatory funnel, with distilled water washing three times, extracting impurities, and removes moisture with calcium chloride.Chloroform is removed in water-free solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.
With the crystal filtration under diminished pressure final vacuum drying of separating out, obtain 49.2 gram triazine monomers.
(5) polymerization of the polyamide-imides of band cinnamate functional group
Triazine monomers 53.156 grams that will be obtained by (4) of preparation example 5-1 are inserted in the round-bottomed flask that is filled with nitrogen, and are dissolved in 400 milliliters of oxolanes.20.238 gram triethylamines are added in the solution.
10.15 gram terephthalyl chlorides are dissolved in 100 milliliters of anhydrous tetrahydro furans, slowly pour in the solution that is dissolved with above-mentioned triazine monomers and triethylamine, vigorous stirring was reacted 6 hours.Slowly add another kind of solution then, continue reaction 6 hours, described another kind of solution is 10.9 grams 1,2,4, and 5-benzene tertacarbonic acid dianhydride is dissolved in 100 milliliters of N-methyl pyrrolidones and the solution that obtains.
After the reaction, the solution that reaction is obtained is slowly poured into and is obtained precipitation in the methyl alcohol, filters dry this polymer of final vacuum.The polymer that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, this step repeats twice, and then vacuum drying obtains 40.1 at last and restrains the polyamide-imides that utilizes triazine ring and have cinnamate functional group.
Preparation example 5-2: the photosensitive polyamide-acid imide of band chalcone group side chain
(1) chalcone light sensitivity group is synthetic
10 gram 4-methoxyl group chalcones and 2.05 gram Cymags are dissolved in 100 milliliters of dimethyl sulfoxide (DMSO)s, reacted 24 hours.After the reaction, the solution that reaction is obtained mixes with chloroform, mixes with distilled water then, stirs, with extracting impurities.Removing behind the water at room temperature reduces pressure solution removes chloroform.The solid formation of remnants is recrystallized in methyl alcohol, obtains the 4-hydroxyl chalcone that 19.7 grams are used for light reaction after the crystal vacuum drying.
(2) introducing of chalcone functional group on the triazine ring
To insert in the round-bottomed flask that is filled with nitrogen by preparation example 5-2 (1) synthetic 4-hydroxyl chalcone 23.8 grams, and be dissolved in 240 milliliters of anhydrous tetrahydro furans.In this solution, add 2.4 gram sodium hydrides, at room temperature reacted 6 hours.Solution slowly is added drop-wise under-5 ℃ in the cyanuric chloride solution, and vigorous stirring was reacted 24 hours, and the preparation method of described cyanuric chloride solution is that adding 18.4 gram cyanuric chlorides are dissolved in it in 200 milliliters of anhydrous tetrahydro furans then in round-bottomed flask.After the reaction, oxolane is removed in the solution decompression distillation that reaction obtains, then remaining solid formation is dissolved in the chloroform again.In separatory funnel with this solution with distilled water washing three times, extracting impurities, and remove moisture with calcium chloride.Then chloroform is removed in this solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.The thing filtration under diminished pressure final vacuum drying that will be recrystallized obtains the pyrrolotriazine derivatives of 31.3 gram band chalcone functional groups.
(3) synthetic with the triazine monomers of two amine functional groups
To insert in the round-bottomed flask by pyrrolotriazine derivatives 38.6 grams of preparation example 5-2 (2) synthetic band chalcone functional group, and be dissolved in 300 milliliters of chloroforms.In addition, 32.8 gram 4-amino phenols and 12g dissolution of sodium hydroxide in 300 milliliters of distilled water that are dissolved with 3 gram softex kws, are mixed vigorous reaction 24 hours then with above-mentioned pyrrolotriazine derivatives solution.After having reacted, organic solution is separated out, transfers in the separatory funnel, with distilled water washing three times, with extracting impurities.Remove moisture with calcium chloride then.Chloroform is removed in this solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.With the crystal filtration under diminished pressure final vacuum drying of separating out, obtain 48.7 gram triazine monomers.
(4) polymerization of the polyamide-imides of band chalcone functional group
Triazine monomers 53.15 grams that will be obtained by (3) of preparation example 5-2 are inserted in the round-bottomed flask that is filled with nitrogen, and are dissolved in 400 milliliters of anhydrous tetrahydro furans.20.24 gram triethylamines are added in this solution.10.15 gram terephthalyl chlorides are dissolved in 100 milliliters of anhydrous tetrahydro furans, slowly are added drop-wise to then in the above-mentioned solution that is dissolved with triazine monomers and triethylamine, vigorous stirring was reacted 6 hours.Drip another kind of solution then, continue reaction 6 hours, the another kind of solution that is added is 10.9 grams 1,2,4, and 5-benzene tertacarbonic acid dianhydride is dissolved in 100 milliliters of N-methyl pyrrolidones and the solution that obtains.After the reaction, the solution that reaction is obtained is slowly poured into and is obtained precipitation in the methyl alcohol, filters the final vacuum drying.The polymer that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, this step repeats twice, and then vacuum drying obtains the polyamide-imides that 42.2 grams are with chalcone functional groups at last.
Preparation example 5-3: the photosensitive polyamide-acid imide of band cumarin group side chain
(1) introducing of cumarin light sensitivity group
16.2 gram umbelliferones and 2.4 sodium hydrides (NaH) are inserted in the round-bottomed flask that is filled with nitrogen, it is dissolved in 160 milliliters of anhydrous tetrahydro furans then.Vigorous stirring was reacted 6 hours subsequently.Slowly splash into cyanuric chloride solution then under-5 ℃, vigorous stirring was reacted 24 hours, and the compound method of described cyanuric chloride solution is in round-bottomed flask 18.4 gram cyanuric chlorides to be dissolved in 200 milliliters of anhydrous tetrahydro furans.After reaction was finished, oxolane was removed in decompression distillation, then remaining solid formation is dissolved in the chloroform again.This solution is washed three times with extracting impurities with distilled water in separatory funnel, and dehumidify with calcium chloride.In the mixed solvent of carrene and n-hexane, be recrystallized after the distillation of this solution decompression removed chloroform.With the recrystallization thing filtration under diminished pressure final vacuum drying of separating out, obtain the pyrrolotriazine derivatives of 28.2 gram band cumarin functional groups.
(2) synthetic with the triazine monomers of two amine functional groups
To insert in the round-bottomed flask by pyrrolotriazine derivatives 31.1 grams of preparation example 5-3 (1) synthetic band cumarin functional group, and be dissolved in 300 milliliters of chloroforms.With 32.8 the gram 4-amino phenols and 12 the gram dissolution of sodium hydroxide 300 milliliters be dissolved with 3 the gram softex kws distilled water in, mix vigorous reaction 24 hours then with above-mentioned triazine solution.After having reacted, organic solution is separated and moves in the separatory funnel, with distilled water washing three times, with extracting impurities.Remove moisture with calcium chloride then.Chloroform is removed in this solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.With the crystal filtration under diminished pressure final vacuum drying of separating out, obtain 41.6 gram triazine monomers.
(3) polymerization of the polyamide-imides of band cumarin functional group
Triazine monomers 45.54 grams that will be obtained by (2) of preparation example 5-3 are inserted in the round-bottomed flask that is filled with nitrogen, and are dissolved in 400 milliliters of oxolanes.20.24 gram triethylamines are added in this solution.10.15 the gram terephthalyl chloride is dissolved in 100 milliliters of anhydrous tetrahydro furans, slowly is added drop-wise in the above-mentioned solution that is dissolved with triazine monomers and triethylamine, vigorous stirring was reacted 6 hours.Slowly drip another kind of solution then, continue reaction 6 hours, the another kind of solution that is added is 10.9 grams 1,2,4, and 5-benzene tertacarbonic acid dianhydride is dissolved in 100 milliliters of N-methyl pyrrolidones and the solution that obtains.After the reaction, the solution that obtains slowly poured into obtain precipitation in the methyl alcohol, filter the final vacuum drying.The polymer that obtains is dissolved in the oxolane again, precipitates in methyl alcohol then, this step repeats twice, and then vacuum drying obtains 26.7 at last and restrains the polyamide-imides that utilizes triazine ring and have cumarin functional group.
Preparation example 6: the preparation of light-sensitive polyamic
Preparation example 6-1: the preparation of the light-sensitive polyamic of band cinnamate group side chain
(1) introducing of cinnamate functional group
18.4 gram cyanuric chlorides are placed the round-bottomed flask that is filled with nitrogen, and be dissolved in 200 milliliters of anhydrous tetrahydro furans.After in this solution, adding 15.2 gram triethylamines, temperature is reduced to-5 ℃, on one side vigorous stirring, slowly drip cinnamoyl chloride solution on one side, reacted 12 hours, described cinnamoyl chloride solution is with the solution after 20 milliliters of anhydrous tetrahydro furan dilutions.
The distillation of the solution decompression that obtains after the reaction, remove oxolane after, be dissolved in again in the carrene, filter with the filter that is filled with silica gel, decompression distillation removes and desolvates.
At last, in the ratio of carrene and n-hexane is 1: 1 mixed solvent, be recrystallized, this solution decompression is filtered.With the solid formation vacuum drying that obtains, obtain 25 gram 2-cinnamoyls-4,6-two chloro-1,3,5-triazines.
(2) synthetic with the triazine monomers of two amine functional groups
The 2-cinnamoyl-4 that will obtain by (1) of preparation example 6-1,6-two chloro-1,3,5-triazines 29.6 grams are inserted in the round-bottomed flask, and by 300 milliliters of chloroform dissolvings.In 300 milliliters of distilled water that are dissolved with 3 gram softex kws, then with above-mentioned 2-cinnamoyl-4,6-two chloro-1,3,5-triazines solution mix, vigorous reaction 24 hours with 32.8 gram 4-amino phenols and 12g dissolution of sodium hydroxide.After having reacted, organic solution is separated out, the solution that obtains of reaction moves in the separatory funnel, with distilled water washing three times, extracting impurities, and removes moisture with calcium chloride.Chloroform is removed in the distillation of solution decompression after dewatering, in the mixed solvent of carrene and n-hexane, be recrystallized then.
With the crystal filtration under diminished pressure final vacuum drying of separating out, obtain 40 gram triazine monomers.
(3) polymerization of the polyamic acid of band cinnamic acid functional group
Triazine monomers 44.144 grams that will be obtained by (2) of preparation example 6-1 are inserted in the round-bottomed flask that is filled with nitrogen, and by 250 milliliters of N-methyl pyrrolidone dissolvings.
With 21.8 grams 1,2,4,5-benzene tertacarbonic acid dianhydride is dissolved in 50 milliliters of N-methyl pyrrolidones, then it slowly is added drop-wise in another solution that is dissolved with above-mentioned triazine monomers vigorous stirring, reacted 24 hours, and obtained the precursor polyamic acid solution of photo-sensistive polyimide.
Preparation example 6-2: the preparation of the light-sensitive polyamic of band chalcone group side chain
(1) chalcone light sensitivity group is synthetic
10 gram 4-methoxyl group chalcones and 2.05 gram Cymags are dissolved in 100 milliliters of dimethyl sulfoxide (DMSO)s, reacted 24 hours.After the reaction, the solution that reaction is obtained mixes with chloroform, mixes with distilled water then, stirs, with extracting impurities.After removing water, this solution at room temperature reduced pressure remove chloroform.The solid formation of remnants is recrystallized in methyl alcohol, obtains 20 gram 4-hydroxyl chalcones after the solid vacuum drying.
(2) introducing of chalcone functional group on the triazine ring
To insert in the round-bottomed flask that is filled with nitrogen by preparation example 6-2 (1) synthetic 4-hydroxyl chalcone 23.8 grams, and be dissolved in 240 milliliters of anhydrous tetrahydro furans.In this solution, add 2.4 gram sodium hydrides, at room temperature reacted 6 hours.With this solution in the cyanuric chloride solution that slowly is added drop-wise under-5 ℃ in round-bottomed flask, vigorous stirring, reacted 24 hours, the preparation method of described cyanuric chloride solution is that 18.4 gram cyanuric chlorides are placed round-bottomed flask and are dissolved in 200 milliliters of anhydrous tetrahydro furans.After the reaction, oxolane is removed in the solution decompression distillation that reaction obtains, then residual solid is dissolved in the chloroform again.In separatory funnel with this solution with distilled water washing three times, extracting impurities, and remove moisture with calcium chloride.Then chloroform is removed in this solution decompression distillation, in the mixed solvent of carrene and n-hexane, be recrystallized then.The thing filtration under diminished pressure final vacuum drying that will be recrystallized obtains the pyrrolotriazine derivatives of 34 gram band chalcone functional groups.
(3) synthetic with the triazine monomers of two amine functional groups
To insert in the round-bottomed flask by pyrrolotriazine derivatives 38.6 grams of preparation example 6-2 (2) synthetic band chalcone functional group, and by 300 milliliters of chloroform dissolvings.In addition, 32.8 gram 4-amino phenols and 12g dissolution of sodium hydroxide in 300 milliliters of distilled water that are dissolved with 3 gram softex kws, are mixed vigorous reaction 24 hours then with above-mentioned triazine solution.After having reacted, organic solution is separated and is transferred to separatory funnel, with distilled water washing three times, extracting impurities.Remove moisture with calcium chloride then.Chloroform is removed in the solution decompression distillation of removing moisture, in the mixed solvent of carrene and n-hexane, be recrystallized then.With the crystal filtration under diminished pressure final vacuum drying of separating out, obtain 45 gram triazine monomers.
(4) polymerization of the polyamic acid of band chalcone functional group
Triazine monomers 53.15 grams that will be obtained by (3) of preparation example 6-2 are inserted in the round-bottomed flask that is filled with nitrogen, then with 260 milliliters of N-methyl pyrrolidone dissolvings.
Dissolving 21.8 grams 1,2,4 in 50 milliliters of N-methyl pyrrolidones, behind the 5-benzene tertacarbonic acid dianhydride, this solution slowly is added drop-wise in the solution that is dissolved with above-mentioned triazine monomers, simultaneously vigorous stirring, reacted 24 hours, and obtained the precursor polyamic acid solution of photo-sensistive polyimide.
Preparation example 6-3: the preparation of the light-sensitive polyamic of band cumarin group side chain
(1) introducing of cumarin light sensitivity group
16.2 gram umbelliferones and 2.4 sodium hydrides (NaH) are inserted in the round-bottomed flask that is filled with nitrogen, it is dissolved in 160 milliliters of anhydrous tetrahydro furans then.Subsequently, this solution of vigorous stirring reacted 6 hours.Slowly add in the cyanuric chloride solution down at-5 ℃ then, vigorous stirring was reacted 24 hours, and the preparation method of described cyanuric chloride solution is in round bottom burns 18.4 gram cyanuric chlorides to be dissolved in 200 milliliters of anhydrous tetrahydro furans.After reaction was finished, oxolane was removed in decompression distillation, then residual solid is dissolved in the chloroform again.In separatory funnel, wash this solution three times,, and dehumidify with calcium chloride with extracting impurities with distilled water.After the distillation of this solution decompression removed chloroform, in the mixed solution of carrene and n-hexane, be recrystallized.The recrystallization thing filtration under diminished pressure final vacuum drying that obtains obtains the pyrrolotriazine derivatives that 29 grams are with cumarin functional groups.
(2) synthetic with the triazine monomers of two amine functional groups
To insert in the round-bottomed flask by pyrrolotriazine derivatives 31.1 grams of preparation example 6-3 (1) synthetic band cumarin functional group, and by 300 milliliters of chloroform dissolvings.With 32.8 the gram 4-amino acid and 12 the gram dissolution of sodium hydroxide 300 milliliters be dissolved with 3 the gram softex kws distilled water in, mix vigorous reaction 24 hours then with above-mentioned triazine solution.After having reacted, organic solution is separated and moves in the separatory funnel, with distilled water washing three times, with extracting impurities.Remove moisture with calcium chloride then.Chloroform is removed in the solution decompression distillation of removing moisture, in the mixed solvent of carrene and n-hexane, be recrystallized then.With the crystal filtration under diminished pressure final vacuum drying of separating out, obtain 40 gram triazine monomers.
(3) polymerization of the polyamic acid of band cumarin functional group
Triazine monomers 45.54 grams that will be obtained by (2) of preparation example 6-3 are inserted in the round-bottomed flask that is filled with nitrogen, and are dissolved in 250 milliliters of N-methyl pyrrolidones.
Dissolving 21.8 grams 1,2,4 in 50 milliliters of N-methyl pyrrolidones, behind the 5-benzene tertacarbonic acid dianhydride, this solution slowly is added drop-wise in the solution that is dissolved with above-mentioned triazine monomers, simultaneously vigorous stirring, reacted 24 hours, and obtained the precursor polyamic acid solution of photo-sensistive polyimide.
Embodiment 1～5
The photosensitive polymers of preparation in the preparation example 1 to 5 is dissolved among the NMP, obtains used solution among the embodiment 1～5.With linear velocity be 1 meter/minute glue spreader this solution is coated in thickness is 18 microns copper film surface, form 25 microns coating.At 200 ℃ of solvents of removing in the coating.Ultra violet lamp with the 600W/ inch removes the coating of desolvating, and illumination makes coating generation photo-crosslinking, forms flexible metal clad laminate film.
Embodiment 6
With the light-sensitive polyamic solution linear velocity of preparation in the preparation example 6 be 1 meter/minute glue spreader to be coated in thickness be 18 microns copper film surface, form 25 microns coating.At 200 ℃ of solvents of removing in the coating.Ultra violet lamp with the 600W/ inch removes the coating of desolvating, and illumination makes coating generation photo-crosslinking.Then, the polyamic acid in the coating carries out imidizate under 350 ℃, obtain flexible metal clad laminate film.
Test is by every physical property of the flexible metal clad laminate film of embodiment 1～6 preparation.Test result sees Table 1～6.
Table 1
Embodiment ????1-1 ????1-2 ????1-3 Method
Hot strength ????251MPa ????249.1MPa ????249.5MPa ????IPC-TM-650， ????2.4.19
Percentage elongation ????50％ ????50％ ????50％
Stretch modulus ????4600MPa ????4550MPa ????4500MPa
Peel strength Initially ????1.2kN/m ????1.1kN/m ????1.1kN/m ????JIS?C-5012
After aging ????0.9kN/m ????0.8kN/m ????0.8kN/m 150 ℃, 7 days
Corrosion is shunk ????0.01％ ????0.02％ ????0.02％
Thermal contraction ????-0.01％ ????-0.02％ ????-0.02％
Insulaion resistance ????1.1×10 8MΩ ????1.0×10 8MΩ ????1.0×10 8MΩ ????IPC-TM-650.2.5.9
Specific insulation ????5.0×10 9MΩ·cm ????4.9×10 9MΩ·cm ????5.0×10 9MΩ·cm ????IPC-TM-650，2.5.17
Dielectric strength 〉=5kV/ mil 〉=5kV/ mil 〉=5kV/ mil ????ASTM-D-149
Anti-immersed solder ????400℃ ????400℃ ????400℃ 1 minute, dipping
IPC: U.S.'s electronic circuit interconnection and encapsulation association
Table 2
Embodiment ????2-1 ????2-2 ????2-3 Method
Hot strength ????251MPa ????249.1MPa ????248.5MPa ????IPC-TM-650， ????2.4.19
Percentage elongation ????50％ ????50％ ????50％
Stretch modulus ????4600MPa ????4550MPa ????4500MPa
Peel strength Initially ????1.2kN/m ????1.1kN/m ????1.1kN/m ????JIS?C-5012
After aging ????0.9kN/m ????0.8kN/m ????0.8kN/m 150 ℃, 7 days
Corrosion is shunk ????0.01％ ????0.02％ ????0.02％
Thermal contraction ????-0.01％ ????-0.02％ ????-0.02％
Insulaion resistance ????1.1×10 8MΩ ????1.0×10 8MΩ ????1.0×10 8MΩ ????IPC-TM-650，2.5.9
Specific insulation ????5.0×10 9MΩ·cm ????4.9×10 9MΩ·cm ????5.0×10 9MΩ·cm ????IPC-TM-650，2.5.17
Dielectric strength 〉=5kV/ mil 〉=5kV/ mil 〉=5kV/ mil ????ASTM-D-149
Anti-immersed solder ????400℃ ????400℃ ????400℃ 1 minute, dipping
Table 3
Embodiment ????3-1 ???3-2 ????3-3 Method
Hot strength ????251MPa ???241.7MPa ????248.5MPa ????IPC-TM-650， ????2.4.19
Percentage elongation ????50％ ???50％ ????50％
Stretch modulus ????4825MPa ???4755MPa ????4680MPa
Peel strength Initially ????1.4kN/m ???1.2kN/m ????1.2kN/m ????JIS?C-5012
After aging ????1.0kN/m ???0.9kN/m ????0.9kN/m 150 ℃, 7 days
Corrosion is shunk ????0.01％ ???0.02％ ????0.02％
Thermal contraction ????-0.01％ ???-0.02％ ????-0.02％
Insulaion resistance ????1.2×10 8MΩ ???1.1×10 8MΩ ????1.0×10 8MΩ ????IPC-TM-650，2.5.9
Specific insulation ????5.2×10 9MΩ·cm ???5.0×10 9MΩ·cm ????5.0×10 9MΩ·cm ????IPC-TM-650，2.5.17
Dielectric strength 〉=5kV/ mil 〉=5kV/ mil 〉=5kV/ mil ????ASTM-D-149
Anti-immersed solder ????420℃ ???400℃ ????410℃ 1 minute, dipping
Table 4
Embodiment ????4-1 ????4-2 ???4-3 Method
Hot strength ????254MPa ????248.7MPa ???248.5MPa ????IPC-TM-650， ????2.4.19
Percentage elongation ????50％ ????50％ ???50％
Stretch modulus ????4820MPa ????4750MPa ???4680MPa
Peel strength Initially ????1.4kN/m ????1.2kN/m ???1.2kN/m ????JIS?C-5012
After aging ????1.0kN/m ????0.9kN/m ???0.9kN/m 150 ℃, 7 days
Corrosion is shunk ????0.01％ ????0.02％ ???0.02％
Thermal contraction ????-0.01％ ????-0.02％ ???-0.02％
Insulaion resistance ????1.2×10 8MΩ ????1.1×10 8MΩ ???1.0×10 8MΩ ????IPC-TM-650，2.5.9
Specific insulation ????5.2×10 9MΩ·cm ????5.0×10 9MΩ·cm ???5.0×10 9MΩ·cm ????IPC-TM-650，2.5.17
Dielectric strength 〉=5kV/ mil 〉=5kV/ mil 〉=5kV/ mil ????ASTM-D-149
Anti-immersed solder ????420℃ ????400℃ ???410℃ 1 minute, dipping
Table 5
Embodiment ?5-1 ????5-2 ????5-3 Method
Hot strength ?250MPa ????249.1MPa ????248.9MPa ????IPC-TM-650， ????2.4.19
Percentage elongation ?50％ ????50％ ????50％
Stretch modulus ?4600MPa ????4570MPa ????4600MPa
Peel strength Initially ?1.1kN/m ????1.0kN/m ????1.0kN/m ????JIS?C-5012
After aging ?1.0kN/m ????0.9kN/m ????0.9kN/m 150 ℃, 7 days
Corrosion is shunk ?0.01％ ????0.02％ ????0.02％
Thermal contraction ?-0.01％ ????-0.02％ ????-0.02％
Insulaion resistance ?1.2×10 8MΩ ????1.0×10 8MΩ ????1.1×10 8MΩ ????IPC-TM-650，2.5.9
Specific insulation ?5.0×10 9MΩ·cm ????4.9×10 9MΩ·cm ????5.0×10 9MΩ·cm ????IPC-TM-650，2.5.17
Dielectric strength 〉=5kV/ mil 〉=5kV/ mil 〉=5kV/ mil ????ASTM-D-149
Anti-immersed solder ?400℃ ????400℃ ????400℃ 1 minute, dipping
Table 6
Embodiment ???6-1 ????6-2 ???6-3 Method
Hot strength ???255MPa ????249.7MPa ???249.5MPa ????IPC-TM-650， ????2.4.19
Percentage elongation ???50％ ????50％ ???50％
Stretch modulus ???4800MPa ????4760MPa ???4690MPa
Peel strength Initially ???1.4kN/m ????1.2kN/m ???1.2kN/m ????JIS?C-5012
After aging ???1.0kN/m ????0.9kN/m ???0.9kN/m 150 ℃, 7 days
Corrosion is shunk ???0.01％ ????0.02％ ???0.02％
Thermal contraction ???-0.01％ ????-0.02％ ???-0.02％
Insulaion resistance ???1.2×10 8MΩ ????1.1×10 8MΩ ???1.0×10 8MΩ ????IPC-TM-650，2.5.9
Specific insulation ???5.2×10 9MΩ·cm ????5.0×10 9MΩ·cm ???5.0×10 9MΩ·cm ????IPC-TM-650，2.5.1?7
Dielectric strength 〉=5kV/ mil 〉=5kV/ mil 〉=5kV/ mil ????ASTM-D-149
Anti-immersed solder ???420℃ ????400℃ ???410℃ 1 minute, dipping
In addition, also tested soldering resistance (reflow resistance) (85 ℃, 60% relative humidity, 168 hours+reflux), test result sees Table 7.
Table 7
Embodiment 1-1 ??1-2 ?1-3 ?2-1 ?2-2 ?2-3 ?3-1 ?3-2 3-3 ?4-1 ?4-2 ?4-3 ?5-1 ?6-2 ?5-3 ?6-1 ?6-2 ?6-3
The first round (℃) 260 ??260 ?260 ?260 ?260 ?260 ?270 ?270 270 ?270 ?270 ?270 ?260 ?260 ?260 ?270 ?270 ?270
Second take turns (℃) 260 ??260 ?260 ?260 ?260 ?260 ?260 ?260 260 ?260 ?260 ?260 ?260 ?260 ?260 ?260 ?260 ?260
Third round (℃) 260 ??250 ?260 ?260 ?250 ?260 ?260 ?260 260 ?260 ?260 ?260 ?250 ?250 ?250 ?260 ?260 ?260
As can be seen, the flexible metal clad laminate film among the present invention has good physical property, as dimensional stability from table 1-7.Especially the distortion and the warpage of flexible metal clad laminate film have been reduced.
Below described the present invention in detail, but be to be understood that, although pointed out preferred implementation of the present invention, but only provided detailed description and specific embodiment wherein in illustrative mode, because for a person skilled in the art, describe in detail according to this, various variations within the spirit and scope of the present invention and change are clearly.
Industrial applicibility
Because the crosslinked resin that the flexible insulating film in the flexible metal clad laminate film of the present invention is formed by the photo-crosslinking of photosensitive polymers is formed, therefore this flexible metal clad laminate film has good physical properties such as dimensional stability, and can be out of shape hardly and warpage.Therefore the flexible metal clad laminate film among the present invention can be applied on the miniaturized electronics in the electronics industry.

Claims (33)

1. flexible metal clad laminate film, it comprises:
Metallic film, and
Flexible insulating film, described flexible insulating film is formed by the photo-crosslinking of photosensitive polymers, and described photosensitive polymers has and can crosslinked light sensitivity side chain take place through light radiation.
2. flexible metal clad laminate film as claimed in claim 1, wherein, described light sensitivity side chain is selected from (1a), (2a), (3a) of the structure with following Chemical formula 2 or (4a):
Chemical formula 2
Figure A2004100864320002C1
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
In the chemical formula 3, m and n are respectively 0～10;
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
Figure A2004100864320004C1
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3???-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320005C1
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), 1 and 2 are selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
Figure A2004100864320005C3
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN.
3. flexible metal clad laminate film as claimed in claim 1, wherein, described photosensitive polymers contains the main chain of having introduced triazine ring.
4. flexible metal clad laminate film as claimed in claim 1, wherein, described photosensitive polymers contains the main chain of having introduced triazine ring, and described triazine ring has and can crosslinked light sensitivity side chain take place through light radiation.
5. flexible metal clad laminate film as claimed in claim 4, wherein, described photosensitive polymers comprises the light sensitivity paracyanogen urate of the structure with following Chemical formula 1:
Chemical formula 1
Figure A2004100864320006C1
In the Chemical formula 1, m+n=1,0≤m≤1,0≤n≤1, R 1(1a) from following Chemical formula 2, (2a), (3a) and (4a) middle selection respectively:
Chemical formula 2
Figure A2004100864320006C2
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-?????????????????????????????????????-O((CH 2) nO) m-
In the chemical formula 3, m and n are respectively 0～10,
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
Figure A2004100864320008C1
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320009C1
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), 1 and 2 are selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 1, R 2And R 3Be selected from the structure of following chemical formula 9 respectively:
Chemical formula 9
Figure A2004100864320010C1
In the chemical formula 9, m and n are respectively 0～10, and numeral 1,2,3,4,5,6,7 and 8 is selected from respectively by H, F, Cl, CN, CH 3, OCH 3And CF 3The group of forming, X is selected from H, F, Cl, CN, CH 3, OCH 3Or CF 3, and Y is selected from CH 2, C (CH 3) 2, C (CF 3) 2, O, S, SO 2, CO and CO 2
6. as flexible metal clad laminate film as described in the claim 4, wherein, described photosensitive polymers comprises the light sensitivity polyester of the structure with following Chemical formula 10:
Chemical formula 10
Figure A2004100864320011C1
In the Chemical formula 10, m+n=1,0≤m≤1,0≤n≤1, R 1Be selected from (1a), (2a) in the following Chemical formula 2, (3a) or (4a) respectively:
Chemical formula 2
Figure A2004100864320011C2
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-??????????????????????????????????-O((CH 2) nO) m-
Figure A2004100864320012C1
In the chemical formula 3, m and n are respectively 0～10,
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
Figure A2004100864320013C1
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320013C2
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively,
Chemical formula 6
-A-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), 1 and 2 are selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
Figure A2004100864320014C3
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 10, R 4And R 5From the structure of following Chemical formula 11, select respectively:
Chemical formula 11
-(CA 2) nO-?????????????????????????????????????????????-O((CA 2) nO) m-
Figure A2004100864320015C1
In the Chemical formula 11, m and n are respectively 0～10, and A and numeral 1,2,3,4,5,6,7 and 8 are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 10, R 6And R 7Be selected from the structure of following Chemical formula 12 respectively:
Chemical formula 12
Figure A2004100864320016C1
In the Chemical formula 12, m and n are respectively 0～10.
7. flexible metal clad laminate film as claimed in claim 4, wherein, described photosensitive polymers comprises the light sensitivity polyethers and/or the polythiaether of the structure with following Chemical formula 13:
Chemical formula 13
Figure A2004100864320016C2
In the Chemical formula 13, m+n=1,0≤m≤1,0≤n≤1, and R 1Be selected from (1a), (2a) in the following Chemical formula 2, (3a) or (4a) respectively:
Chemical formula 2
Figure A2004100864320017C1
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-????????????????????????????????????-O((CH 2) nO) m-
Figure A2004100864320018C1
In the chemical formula 3, m and n are respectively 0～10,
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A-(CA 2) nCA 2??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7,
Chemical formula 7
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), 1 and 2 are selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
Figure A2004100864320020C2
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 13, R 8And R 9From the structure of following Chemical formula 14, select respectively:
Chemical formula 14
-(CA 2) n-??????????????????????????????????????????????????????-O(CA 2) n-
Figure A2004100864320020C3
Figure A2004100864320021C1
In the Chemical formula 11, m and n are respectively 0～10, and A and numeral 1,2,3,4,5,6,7 and 8 are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 13, R 10And R 11From the structure of following Chemical formula 15, select respectively:
Chemical formula 15
-O(CA 2) nO-?????????????????????????????????-O((CA 2) mO) nO-
Figure A2004100864320022C1
-S(CA 2) nS-????????????????????????????????????-S((CA 2) mO) nS-
In the Chemical formula 15, m and n are respectively 0～10, and A and numeral 1,2,3,4,5,6,7 and 8 are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming.
8. flexible metal clad laminate film as claimed in claim 4, wherein, described photosensitive polymers comprises the photosensitive polyamide-acid imide of the structure with following Chemical formula 16:
Chemical formula 16
In the Chemical formula 16, m+n=1,0≤m≤1,0≤n≤1, R 1Be selected from (1a), (2a) in the following Chemical formula 2, (3a) or (4a) respectively:
Chemical formula 2
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-?????????????????????????????-O((CH 2) nO) m-
In the chemical formula 3, m and n are respectively 0～10,
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
Figure A2004100864320026C1
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320027C1
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming:
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
Figure A2004100864320027C2
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), numeral 1 and 2 is selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 16, R 12And R 13Respectively based on amine with the structure that is selected from following Chemical formula 17:
Chemical formula 17
-(CH 2) nNH 2???????????????????????????????????-O(CH 2) n-NH 2
In the Chemical formula 17, m and n are respectively 0～10,
In the Chemical formula 16, R 14Based on carboxylic acid dianhydride with the structure that is selected from following Chemical formula 18:
Chemical formula 18
Figure A2004100864320028C2
In the Chemical formula 16, R 15From the structure of following Chemical formula 19, select:
Chemical formula 19
Figure A2004100864320029C1
In the Chemical formula 19, m and n are respectively 0～10.
9. flexible metal clad laminate film as claimed in claim 4, wherein, described photosensitive polymers comprises the photo-sensistive polyimide of the structure with following Chemical formula 20:
Chemical formula 20
In the Chemical formula 20, m+n=1,0≤m≤1,0≤n≤1, R 1Be selected from (1a), (2a), (3a) and the structure (4a) of following Chemical formula 2:
Chemical formula 2
Figure A2004100864320030C1
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-??????????????????????????????-O((CH 2) nO) m-
Figure A2004100864320031C1
In the chemical formula 3, m and n are respectively 0～10;
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
Figure A2004100864320031C2
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320032C1
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320032C2
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
Figure A2004100864320033C1
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), numeral 1 and 2 is selected from the structure of following chemical formula 8 respectively,
Chemical formula 8
-A
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 20, R 16And R 17Respectively based on amine with the structure that is selected from following Chemical formula 17:
Chemical formula 17
-(CH 2) n???????????????????????????????-NH 2-O(CH 2) n-NH 2
In the Chemical formula 17, m and n are respectively 0～10,
In the Chemical formula 20, R 18And R 19Respectively based on carboxylic acid dianhydride with the structure that is selected from following Chemical formula 18:
Chemical formula 18
Figure A2004100864320034C1
10. flexible metal clad laminate film as claimed in claim 1, wherein, the number-average molecular weight Mn of described photosensitive polymers is 1,000 to 1,000,000.
11. flexible metal clad laminate film as claimed in claim 1, wherein, described metallic film is made by a kind of metal of selecting from copper, platinum, gold, silver and aluminium.
12. flexible metal clad laminate film as claimed in claim 1, wherein, the thickness of described metallic film is 0.1～500 micron.
13. flexible metal clad laminate film as claimed in claim 1 wherein, has also formed adhesive phase between described metallic film and the flexible insulating film.
14. flexible metal clad laminate film as claimed in claim 1, wherein, the thickness of described flexible insulating film is 1 nanometer～10 centimetre.
15. a method for preparing flexible metal clad laminate film, this method may further comprise the steps:
(a) photosensitive polymers of preparation band light sensitivity side chain, described light sensitivity side chain can take place crosslinked through light radiation;
(b) described photosensitive polymers is dissolved in prepares solution in the solvent;
(c) described solution is coated in the metallic film surface and forms coating;
(d) the described solvent in the described coating of removal;
(e) irradiation makes described photosensitive polymers crosslinked except that the surface of the coating of desolvating, thereby forms flexible insulating film.
16. a method for preparing flexible metal clad laminate film, this method may further comprise the steps:
(a) photosensitive polymers of preparation band light sensitivity side chain, described light sensitivity side chain can take place crosslinked through light radiation;
(b) described photosensitive polymers is dissolved in prepares solution in the solvent;
(c) described solution is coated in substrate surface and forms coating;
(d) the described solvent in the described coating of removal;
(e) irradiation makes described photosensitive polymers crosslinked except that the surface of the coating of desolvating, thereby forms flexible insulating film;
(f) described flexible insulating film is peeled off from the surface of described substrate; With
(g) flexible insulating film and the metallic film under will peeling off with adhesive is bonded together.
17. as claim 15 or the 16 described methods that prepare flexible metal clad laminate film, wherein, described light sensitivity side chain is selected from (1a), (2a) of structure with following Chemical formula 2, (3a) with (4a):
Chemical formula 2
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-????????????????????????????-O((CH 2) nO) m-
In the chemical formula 3, m and n are respectively 0～10,
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming.
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), numeral 1 and 2 is selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN.
18. as claim 15 or the 16 described methods that prepare flexible metal clad laminate film, wherein, described photosensitive polymers comprises the main chain of having introduced triazine ring.
19. as claim 15 or the 16 described methods that prepare flexible metal clad laminate film, wherein, described photosensitive polymers contains the main chain of having introduced triazine ring, described triazine ring has and can crosslinked light sensitivity side chain take place through light radiation.
20. the method for preparing flexible metal clad laminate film as claimed in claim 19, wherein, described photosensitive polymers comprises the light sensitivity paracyanogen urate of the structure with following Chemical formula 1:
Chemical formula 1
In the Chemical formula 1, m+n=1,0≤m≤1,0≤n≤1, R 1(1a) from following Chemical formula 2, (2a), (3a) and (4a) middle selection respectively:
Chemical formula 2
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-????????????????????????????????-O((CH 2) nO) m-
Figure A2004100864320040C1
In the chemical formula 3, m and n are respectively 0～10,
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320041C2
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A-(CA 2) nCA 3??-O(CA 2) nCA 3-??(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
Figure A2004100864320042C2
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), numeral 1 and 2 is selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 1, R 2And R 3Be selected from the structure of following chemical formula 9 respectively:
Chemical formula 9
In the chemical formula 9, m and n are respectively 0～10, and numeral 1,2,3,4,5,6,7 and 8 is selected from respectively by H, F, Cl, CN, CH 3, OCH 3And CF 3The group of forming, X is selected from H, F, Cl, CN, CH 3, OCH 3Or CF 3, and Y is selected from CH 2, C (CH 3) 2, C (CF 3) 2, O, S, SO 2, CO and CO 2
21. the method for preparing flexible metal clad laminate film as claimed in claim 19, wherein, described photosensitive polymers comprises the light sensitivity polyester of the structure with following Chemical formula 10:
Chemical formula 10
Figure A2004100864320044C1
In the Chemical formula 10, m+n=1,0≤m≤1,0≤n≤1, R 1Be selected from (1a), (2a) in the following Chemical formula 2, (3a) or (4a) respectively:
Chemical formula 2
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-??????????????????????????-O((CH 2) nO) m-
In the chemical formula 3, m and n are respectively 0～10,
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320047C1
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), numeral 1 and 2 is selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
Figure A2004100864320047C3
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 10, R 4And R 5From the structure of following Chemical formula 11, select respectively:
Chemical formula 11
-(CA 2) nO-?????????????????????????????????????-O((CA 2) nO) m-
Figure A2004100864320048C1
In the Chemical formula 11, m and n are respectively 0～10, and A and numeral 1,2,3,4,5,6,7 and 8 are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 10, R 6And R 7Be selected from the structure of following Chemical formula 12 respectively:
Chemical formula 12
In the Chemical formula 12, m and n are respectively 0～10.
22. the method for preparing flexible metal clad laminate film as claimed in claim 19, wherein, described photosensitive polymers comprises the light sensitivity polyethers and/or the polythiaether of the structure with following Chemical formula 13:
Chemical formula 13
Figure A2004100864320049C2
In the Chemical formula 13, m+n=1,0≤m≤1,0≤n≤1, and R 1Be selected from (1a), (2a) in the following Chemical formula 2, (3a) or (4a) respectively:
Chemical formula 2
Figure A2004100864320050C1
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-?????????????????????????-O((CH 2) nO) m-
Figure A2004100864320051C1
In the chemical formula 3, m and n are respectively 0～10;
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
Figure A2004100864320052C1
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively,
Chemical formula 5
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
Figure A2004100864320053C2
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), numeral 1 and 2 is selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 13, R 8And R 9From the structure of following Chemical formula 14, select respectively,
Chemical formula 14
-(CA 2) n-???????????????????????????????????????????????-O(CA 2) n-
Figure A2004100864320054C1
In the Chemical formula 14, m and n are respectively 0～10, and A and numeral 1,2,3,4,5,6,7 and 8 are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 13, R 10And R 11From the structure of following Chemical formula 15, select respectively:
Chemical formula 15
-O(CA 2) nO-????????????????????????????????-O((CA 2) mO) nO-
-S(CA 2) nS-??????????????????????????????????-S((CA 2) mO) nS-
In the Chemical formula 15, m and n are respectively 0～10, and A and numeral 1,2,3,4,5,6,7 and 8 are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming.
23. the method for preparing flexible metal clad laminate film as claimed in claim 19, wherein, described photosensitive polymers comprises the photosensitive polyamide-acid imide of the structure with following Chemical formula 16:
Chemical formula 16
Figure A2004100864320057C1
In the Chemical formula 16, m+n=1,0≤m≤1,0≤n≤1, R 1Be selected from (1a), (2a) in the following Chemical formula 2, (3a) or (4a) respectively:
Chemical formula 2
Figure A2004100864320057C2
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-???????????????????????????????-O((CH 2) nO) m-
Figure A2004100864320058C1
In the chemical formula 3, m and n are respectively 0～10;
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), numeral 1 and 2 is selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 16, R 12And R 13Respectively based on amine with the structure that is selected from following Chemical formula 17:
Chemical formula 17
-(CH 2) n-NH 2????????????????????????????????-O(CH 2) n-NH 2
In the Chemical formula 17, m and n are respectively 0～10,
In the Chemical formula 16, R 14For based on carboxylic acid dianhydride with the structure that is selected from following Chemical formula 18:
Chemical formula 18
Figure A2004100864320061C2
In the Chemical formula 16, R 15From the structure of following Chemical formula 19, select,
Chemical formula 19
In the Chemical formula 19, m and n are respectively 0～10.
24. a method for preparing flexible metal clad laminate film, this method may further comprise the steps:
(a) the light-sensitive polyamic solution of preparation band light sensitivity side chain, described light sensitivity side chain can take place crosslinked through light radiation;
(b) described solution is coated in the metallic film surface and forms coating;
(c) solvent in the described coating of removal;
(d) polyamic acid that removes in the coating of desolvating is carried out imidizate, thereby form photo-sensistive polyimide; With
(e) before or after step (d), shine the surface of described coating,, thereby form flexible insulating film so that described photo-sensistive polyimide is crosslinked.
25. a method for preparing flexible metal clad laminate film, this method may further comprise the steps:
(a) the light-sensitive polyamic solution of preparation band light sensitivity side chain, described light sensitivity side chain can take place crosslinked through light radiation;
(b) described solution is coated in substrate surface, to form coating;
(c) solvent in the described coating of removal;
(d) polyamic acid that removes in the coating of desolvating is carried out imidizate, thereby form photo-sensistive polyimide;
(e) before or after step (d), shine the surface of described coating,, thereby form flexible insulating film so that described photo-sensistive polyimide is crosslinked;
(f) with the sur-face peeling of described flexible insulating film from described substrate;
(g) flexible insulating film and the metallic film under will peeling off with adhesive is bonded together.
26. as claim 24 or the 25 described methods that prepare flexible metal clad laminate film, wherein, described light sensitivity side chain is selected from (1a), (2a), (3a) of the structure with following Chemical formula 2 or (4a):
Chemical formula 2
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-??????????????????????-O((CH 2) nO) m-
Figure A2004100864320064C1
In the chemical formula 3, m and n are respectively 0～10;
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
Figure A2004100864320065C1
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3????-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320066C1
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
Figure A2004100864320066C2
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), numeral 1 and 2 is selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
Figure A2004100864320066C3
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN.
27. as claim 24 or the 25 described methods that prepare flexible metal clad laminate film, wherein, described photosensitive polymers contains the main chain of having introduced triazine ring.
28. as claim 24 or the 25 described methods that prepare flexible metal clad laminate film, wherein, described photosensitive polymers contains the main chain of having introduced triazine ring, has on the described triazine ring and can crosslinked light sensitivity side chain take place through light radiation.
29. the method for preparing flexible metal clad laminate film as claimed in claim 28, wherein, described photo-sensistive polyimide comprises the structure of following Chemical formula 20:
Chemical formula 20
In the Chemical formula 20, m+n=1,0≤m≤1,0≤n≤1, R 1(1a) from following Chemical formula 2, (2a), (3a) and (4a) middle selection respectively:
Chemical formula 2
Figure A2004100864320067C2
In the Chemical formula 2 (1a), X selects from the structure of following chemical formula 3:
Chemical formula 3
-((CH 2) nO) m-??????????????????????????-O((CH 2) nO) m-
In the chemical formula 3, m and n are respectively 0～10,
In the Chemical formula 2 (1a), Y selects from the structure of following chemical formula 4:
Chemical formula 4
In the chemical formula 4, numeral 1,2,3,4,5,6,7,8 and 9 is selected from the structure of following chemical formula 5 respectively:
Chemical formula 5
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320069C2
In the chemical formula 5, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
Chemical formula 2 (2a) and (3a) in, n is 0～10, the structure that numeral 1,2,3,4 and 5 is selected from following chemical formula 6 respectively:
Chemical formula 6
-A??-(CA 2) nCA 3??-O(CA 2) nCA 3??-(O(CA 2) m) nCA 3??-O(CA 2) nOCA 3??-(O(CA 2) m) nOCA 3
Figure A2004100864320070C1
In the chemical formula 6, m and n are respectively 0～10, and A, B, C, D and E are selected from respectively by H, F, Cl, CN, CF 3And CH 3The group of forming,
In the Chemical formula 2 (4a), Y is selected from the structure of following chemical formula 7:
Chemical formula 7
In the chemical formula 7, n is 0～10,
In the Chemical formula 2 (4a), numeral 1 and 2 is selected from the structure of following chemical formula 8 respectively:
Chemical formula 8
-A
In the chemical formula 8, A is selected from H, F, CH 3, CF 3Or CN,
In the Chemical formula 20, R 16And R 17Respectively based on amine with the structure that is selected from following Chemical formula 17:
Chemical formula 17
-(CH 2) n-NH 2??????????????????????????????-O(CH 2) n-NH 2
Figure A2004100864320071C1
In the Chemical formula 17, m and n are respectively 0～10,
In the Chemical formula 20, R 18And R 19Respectively based on carboxylic acid dianhydride with the structure that is selected from following Chemical formula 18:
Chemical formula 18
30. as claim 15,16, the 24 or 25 described methods that prepare flexible metal clad laminate film, wherein, described metallic film is made by a kind of metal that is selected from copper, platinum, gold, silver and aluminium.
31. as claim 15,16, the 24 or 25 described methods that prepare flexible metal clad laminate film, wherein, the thickness of described metallic film is 0.1～500 micron.
32. as claim 15,16, the 24 or 25 described methods that prepare flexible metal clad laminate film, wherein, the thickness of described flexible insulating film is 1 nanometer～10 centimetre.
33. as claim 15,16, the 24 or 25 described methods that prepare flexible metal clad laminate film, wherein, the number-average molecular weight Mn of described photosensitive polymers is 1,000 to 1,000,000.
CNA2004100864325A 2004-05-28 2004-10-20 Flexible metal clad laminate film and a manufacturing method for the same Pending CN1701953A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102112520B (en) * 2008-06-16 2014-01-15 乔治亚技术研究公司 Thermally crosslinked polymeric compositions and methods of making the same
CN109071814A (en) * 2016-04-11 2018-12-21 Skc株式会社 Colorless and transparent polyamide-imides film and preparation method thereof
CN110950851A (en) * 2019-12-05 2020-04-03 营口理工学院 Triazinyl coumarin type fluorescent whitening agent and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
KR100822838B1 (en) 2004-10-25 2008-04-17 주식회사 코오롱 Preparation of flexible copper-clad laminate having photosensitive layer
WO2014088293A1 (en) * 2012-12-04 2014-06-12 한국화학연구원 Novel polyimide polymer, method of preparing same, and organic insulation layer using same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102112520B (en) * 2008-06-16 2014-01-15 乔治亚技术研究公司 Thermally crosslinked polymeric compositions and methods of making the same
CN109071814A (en) * 2016-04-11 2018-12-21 Skc株式会社 Colorless and transparent polyamide-imides film and preparation method thereof
CN109071814B (en) * 2016-04-11 2023-12-01 爱思开迈克沃有限公司 Colorless transparent polyamide-imide film and preparation method thereof
CN110950851A (en) * 2019-12-05 2020-04-03 营口理工学院 Triazinyl coumarin type fluorescent whitening agent and preparation method and application thereof
CN110950851B (en) * 2019-12-05 2023-03-21 营口理工学院 Triazinyl coumarin type fluorescent whitening agent and preparation method and application thereof

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