CN100512602C - Adhesive and adhesive film - Google Patents
Adhesive and adhesive film Download PDFInfo
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- CN100512602C CN100512602C CNB2004100421473A CN200410042147A CN100512602C CN 100512602 C CN100512602 C CN 100512602C CN B2004100421473 A CNB2004100421473 A CN B2004100421473A CN 200410042147 A CN200410042147 A CN 200410042147A CN 100512602 C CN100512602 C CN 100512602C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Abstract
本发明的粘接剂和粘接性薄膜含有具有如通式I：(R和Φ如说明书中所记载)所示的重复单元的聚酰亚胺。本发明的粘接剂和粘接性薄膜具有良好的粘接性、耐热性、挠性和高频范围内的介电特性。
The adhesive and adhesive film of the present invention contain polyimide having a repeating unit represented by general formula I: (R and Φ are as described in the specification). The adhesive and adhesive film of the present invention have good adhesiveness, heat resistance, flexibility and dielectric properties in the high frequency range.
Description
Technical field
The present invention relates to good bonding agent of thermal endurance and cementability and adhered thin film.
Background technology
In the past, the bonding agent of fields uses such as electronic electric equipment, universe aviation machine, Transport Machinery or adhered thin film mainly were epoxy system or acrylic acid series bonding agent.But these resins have restricted processing conditions, the service condition of back operation because of poor heat resistance causes the thermal endurance deficiency of the product after bonding.
Therefore, people wish to obtain the bonding agent and the adhered thin film of good heat resistance, such as there being the people to disclose the method that the polyimide based resin dispersion liquid is coated on the base material, forms thermocompression bonded mould assembly adhesive linkage as bonding agent.This adhesive linkage heat pressure adhesive to by on the sticky object (as, the spy opens clear 61-143477 communique).The somebody disclose with the polyimide based resin dispersion liquid be coated in film form with after on the carrier with solvent evaporation, form the method for thermocompression bonded mould assembly adhered thin film.This kind adhered thin film is clipped in by between the sticky object, carry out heat pressure adhesive (as, the spy opens flat 5-179224 communique).
But these polyimide bonding agents, the used polyimide resin of adhered thin film are insoluble to solvent usually.Therefore, if bonding agent, then the solution of its precursor substance polyamic acid must be coated in, remove and desolvate, and at high temperature carry out imidizate and handle by after on the sticky object, complex operation not only, and can cause by problems such as the heat ageing of sticky object and thermal deformations.If adhered thin film, then must remove and desolvate and at high temperature carry out imidizate and handle and could form film, complex operation not only, and the problem of the expensive equipment of needs input is arranged.
In order to overcome the above problems, the someone developed the bonding agent that the solution of the polyimide resin that dissolves in solvent makes (as, the spy opens flat 5-306387 communique).
In recent years, in electric industry, people wish in the electric insulation layer filming to shorten by the dielectric constant that reduction contains the whole insulating barrier of adhesive linkage the time of delay of signaling rate.
Yet above-mentioned adhesion type polyimides in the past is an aromatic polyimide, though their shortcoming be dielectric constant when 10GHz according to the difference of aromatic ring content and different, be up to about 3.5.
Generally by in the monomer of forming macromolecular material, using the aliphatic category material to reduce dielectric constant.Employing non-aromatic tetracarboxylic dianhydrides such as the present inventor have carried out the synthetic of polyimides.The non-aromatic tetracarboxylic dianhydride can enumerate 1,2,3, aliphat (chain) tetracarboxylic dianhydrides, 1,2 such as 4-butane tetracarboxylic acid dianhydride, 3,4-cyclobutane tetracarboxylic dianhydride, 1,2,4,5-pentamethylene tetracarboxylic dianhydride, two ring [2.2.2] suffering-7-alkene-2,3,5, alicyclic tetracarboxylic dianhydrides such as 6-tetracarboxylic dianhydride.But, with the non-constant of polyimides thermal endurance that aliphat (chain) tetracarboxylic dianhydride obtains, make thermal endurance deficiency after bonding, poor practicability.And if use alicyclic tetracarboxylic dianhydride, what obtain is polyimides than chain thing good heat resistance.With 1,2,3, the polyimides that 4-cyclobutane tetracarboxylic dianhydride obtains is because poorly soluble in organic solvent, thus must use the precursor of polyimides be polyamic acid solution as bonding agent or adhered thin film formation liquid, fail to address the above problem.And, if use 1,2,4,5-pentamethylene tetracarboxylic dianhydride, two ring [2.2.2] suffering-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, although can obtain being soluble in the polyimides of organic solvent, but coat the film flexibility deficiency that polyimides obtains, such as be not useable for making flexible print circuit board such to the flexible product that requirement is arranged, poor practicability.
Summary of the invention
Purpose of the present invention be exactly the problem that can solve in the past the polyimides as bonding agent or adhered thin film and exist will be provided, dissolve in solvent, good heat resistance, flexible good, thermocompression bonded mould assembly bonding agent and adhered thin film that dielectric constant is low.
Inventors of the present invention have carried out deep discussion for overcoming the above problems, and found that the polyimides with specific cycloaliphatic ring tetrabasic carboxylic acid structure is suitable as thermocompression bonded mould assembly bonding agent and adhered thin film very much, thereby have finished the present invention.
The invention provides the bonding agent of the organic solvent solution formation that contains polyimides, polyimides wherein has general formula I exactly:
(the 4 valency groups that R comes for being derived by cyclohexane, Φ are that carbon number is the group that 2～39 divalent fatty group, alcyl, aromatic radical or they combine, also can have on the main chain of Φ to be selected from-O-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-,-OSi (CH
3)
2-,-C
2H
4O-,-at least 1 group among the S-) shown in repetitive.
The cementability polyimide film that the present invention also provides above-mentioned polyimides to form.
The glass transition temperature of above-mentioned polyimides is preferred below 350 ℃, and the dielectric constant during 10GHz is preferred below 3.2.
Embodiment
Be used for polyimides of the present invention and have repetitive shown in following general formula I:
Wherein, the 4 valency groups that come for deriving of R by cyclohexane.Φ is that carbon number is the group that 2～39 divalent fatty group, alcyl, aromatic radical or they combine.Also can have on the main chain of Φ be selected from-O-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-,-OSi (CH
3)
2-,-C
2H
4O-,-groups such as S-.
Preferred Φ can enumerate: the fatty group of polyalkylene, polyoxy alkylidene, xylylene and their alkyl substituent, halogen substituent etc., cyclohexane, dicyclohexyl methyl hydride, dimethyl cyclohexane, isophorone, norbornane and their alkyl substituent, halogen substituent etc. are derived and next divalent alcyl, and benzene, naphthalene, biphenyl, diphenyl-methane, diphenyl ether, diphenyl sulphone (DPS), benzophenone and their alkyl substituent, halogen substituent etc. are derived and next divalent aromatic radical.More specifically, can enumerate the divalent group that following structural formula is represented.
The content of the repetitive shown in the general formula I preferably accounts for 10～100 moles of % of total repetition unit, more preferably 50～100 moles of %.Also have, the number of the repetitive shown in general formula I that is contained in 1 polyimide molecule, is more preferably 20～200 by preferred 10～2000.
Polyimides A is with the reaction of tetrabasic carboxylic acid composition and diamines constituents (diamines and derivative thereof) and get.Can enumerate cyclohexane tetrabasic carboxylic acid, cyclohexane tetrabasic ester class, cyclohexane tetracarboxylic dianhydride etc. as the tetrabasic carboxylic acid composition, preferred cyclohexane tetracarboxylic dianhydride.Should illustrate that above-mentioned tetrabasic carboxylic acid composition comprises position isomer.
The polyimides A that contains the cyclohexane tetrabasic carboxylic acid skeleton that is come by above-mentioned tetrabasic carboxylic acid composition is easy to macromolecule and quantizes, solubility in organic solvent is also enough high, therefore after polyimides A being smeared as bonding agent, be easy to just can form the flexible adhesive linkage that enough thickness is arranged again and have durability.And the shaping processing of making film is also easy, is favourable.
At the solvent soluble that does not damage polyimides A, the flexibility of film, heat pressure adhesive, under the prerequisite of high frequency performance, the tetrabasic carboxylic acid composition can contain other tetrabasic carboxylic acid or derivatives thereofs as being selected from PMA, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 2,3,3 ', 4 '-bibenzene tetracarboxylic, 2,2-two (3,4-dicarboxyl phenyl) propane, 2, two (2, the 3-dicarboxyl phenyl) propane of 2-, 2, two (3,4-dicarboxyl phenyl)-1,1 of 2-, 1,3,3, the 3-HFC-236fa, 2, two (2,3-dicarboxyl phenyl)-1 of 2-, 1,1,3,3, the 3-HFC-236fa, two (3,4-dicarboxyl phenyl) sulfone, two (3,4-dicarboxyl phenyl) ether, two (2,3-dicarboxyl phenyl) ether, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, 2,2 ', 3,3 '-benzophenone tetrabasic carboxylic acid, 4,4 '-(right-phenylene dioxy base)-two phthalic acids, 4,4 '-(-phenylene dioxy base)-two phthalic acids, the ethylidene tetrabasic carboxylic acid, 1,2,3, the 4-BTCA, 1,2,3,4-cyclobutane tetrabasic carboxylic acid, 1,2,4,5-pentamethylene tetrabasic carboxylic acid, 3-carboxymethyl-1,2,4-pentamethylene tricarboxylic acids, two ring [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetrabasic carboxylic acid, the dicyclohexyl tetrabasic carboxylic acid, 1, two (2, the 3-dicarboxyl phenyl) ethane of 1-, two (2,3-dicarboxyl phenyl) methane, two (3,4-dicarboxyl phenyl) methane, at least a compound in their derivative.
The diamines constituents can be enumerated diamines, vulcabond, diaminourea dimethylamino silane class etc., but preferred diamines.Diamine contents in the diamines constituents, preferred 50 moles of % above (comprising 100 moles of %).
Above-mentioned diamines can be an aliphatic diamine, also can be aromatic diamine, also can be their mixture.But " aromatic diamine " among the present invention is meant the diamines of amino and aromatic ring Direct Bonding, and its part-structure also can comprise fatty group, alcyl, other substituting groups." aliphatic diamine " is meant the diamines of amino and fatty group or alcyl Direct Bonding, and its part-structure also can comprise aromatic ring yl, other substituting groups.
Generally speaking, if use aliphatic diamine, then, be difficult to obtain the polyimides of HMW because intermediate product polyamic acid and aliphatic diamine form firm complex as constituent.Therefore, must adopt has higher deliquescent solvent to complex, as means such as cresols.But, if use cyclohexane tetrabasic carboxylic acid or derivatives thereof and aliphatic diamine, be polyamic acid and the more weak complex of aliphatic diamine bonding then, so the easy macromolecule of polyimides quantizes owing to what form as constituent.
Above-mentioned aliphatic diamine, can enumerate as 4,4 '-diamino-dicyclohexyl methane, ethylenediamine, hexamethylene diamine, two (3-aminopropyl) ethers of polyethylene glycol, two (3-aminopropyl) ethers, 1 of polypropylene glycol, two (amino methyl) cyclohexanes, 1 of 3-, two (amino methyl) cyclohexanes of 4-, MXDP, terephthaldehyde's base diamines, IPD, norbornane diamines, siloxane diamine etc.
Above-mentioned aromatic diamine can be enumerated as 4,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl sulfone, m-phenylene diamine (MPD), p-phenylenediamine (PPD), diaminobenzophenone, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene etc.
Polyimides A among the present invention makes organic solvent solution usually.As organic solvent, can enumerate N-N-methyl-2-2-pyrrolidone N-, N, N-dimethylacetylamide, N, dinethylformamide, methyl-sulfoxide, hempa acid amide, sulfolane, parachlorophenol, metacresol, gamma-butyrolacton, propylene carbonate, dioxane, 2-chloro-4-hydroxy-methylbenzene etc.
The organic solvent solution of the polyimides A that bonding agent of the present invention is used is obtained by following (i)～(iii) method.
(i) in the organic solvent solution of diamines constituents, add the tetrabasic carboxylic acid composition, or in the organic solvent solution of tetrabasic carboxylic acid composition, add the diamines constituents, preferred below 80 ℃, especially under near room temperature or the temperature below the room temperature, kept 0.5～3 hour.Add azeotropic dehydration solvents such as toluene or dimethylbenzene in the reaction intermediate polyamic acid solution that obtains, the water that produces is rejected to system by azeotropic carries out dehydration outward, obtain the organic solvent solution of polyimides A.
(ii) add dehydrating agent such as acetic anhydride in the polyamic acid solution of reaction intermediate and make its imidizate, add the solvents low such as methyl alcohol then, make polyimides A precipitation the solvability of polyimides A.Through filtration, cleaning, drying solid constituent is separated, and then it is dissolved in N, in the N-dimethylacetylamide equal solvent, obtain the organic solvent solution of polyimides A.
(iii), keep making its imidizate in 3～12 hours down, add the solvents low such as methyl alcohol then, make polyimides A precipitation the solvability of polyimides A at 150～220 ℃ with high boiling solvents such as cresols preparation polyamic acid solution.Through filtration, cleaning, drying solid constituent is separated, and then it is dissolved in N, in the N-dimethylacetylamide equal solvent, obtain the organic solvent solution of polyimides A.
If polyimides A concentration contained in the organic solvent solution of polyimides A is low excessively, will cause bonding agent to be coated in the thickness low LCL of the adhesive linkage that the back forms on the base material, adhesive strength reduces, so not preferred.And if polyimides A excessive concentration will cause viscosity height, the coating difficulty of bonding agent, so also not preferred.Preferred polyimides concentration range is 1～50 weight %, preferred especially 5～30 weight %.
Cementability polyimide film of the present invention, obtain by the following method, the organic solvent solution of the polyimides A that will obtain with above-mentioned (i)～(iii) method is applied on the supports such as glass plate, metallic plate exactly, heating makes organic solvent evaporation under 200～350 ℃, the film that forms is peeled off from support again.
In addition, also the organic solvent solution of polyamic acid can be coated on the supports such as glass plate, metallic plate, make it that dehydration imidization reaction take place 200～350 ℃ of following heating, make polyimide film by this method, but the organic solvent solution of preferred polyimides is because it can further bring into play characteristics of the present invention.
If the thickness of cementability polyimide film is thin excessively, will cause can not cover by the concavo-convex place on the surface of sticky object when bonding, make that bond area is little, adhesive strength is low, therefore not preferred.And if the thickness of cementability polyimide film is blocked up, will cause that film can not make adhesive strength inhomogeneous by uniformly softening when bonding, adhering resin when bonding (polyimide resin) flows out, and is therefore also not preferred.The thickness of polyimide film is according to different and different by the surface configuration of sticky object, but preferred 1～600 μ m, preferred especially 1～200 μ m.
The polyimides A that the present invention is used, the low characteristics of dielectric constant under high frequency are not only arranged, also have the frequency range significant to practical application promptly in 1～20GHz scope the frequency dependence of dielectric constant low and maintain these characteristics of certain value, very preferred as the insulating material of electric and electronic industry.If select the aliphatic diamine of two amines, then its dielectric constant when 10GHz is below 2.8, and is preferred especially.Even the use aromatic diamine also can reach below 3.2.The lower limit of the dielectric constant that can reach is generally 2.6.Polyimides A also has the frequency dependence of the dielectric loss tangent in 1～20GHz scope low simultaneously, maintains these characteristics of certain value in 0.008～0.018 scope, has extremely good high frequency characteristics.
The glass transition temperature of the cementability polyimide film that gets by polyimides A, according to the difference of selected diamines and different, but generally below 350 ℃.Though cementability is different with the residual solvent amount, but to the temperature more than glass transition temperature show, if this moment, extrusion temperature rose so high so glass transition temperature is too high, if cross low then the thermal endurance deficiency of adhesive linkage is not preferred.The scope of preferred glass transition temperature is at 200～350 ℃, preferred especially 250～320 ℃.
Use polyimides A to carry out to carry out according to the following steps when bonding.With the organic solvent solution of polyimides A as adhesive applicating on base material, the evaporation by organic solvent forms adhesive linkage.To be made that on this adhesive linkage base material and adherend bond together by the sticky object heat pressure adhesive.In addition, also can coat bonding agent on the two sides of base material and make it form adhesive linkage, then will be on two-sided adhesive linkage by the sticky object heat pressure adhesive.Can also adopt glass fabric or carbon cloth are immersed in method in the bonding agent (organic solvent solution of polyimides A).
Simultaneously, utilize the organic solvent solution of polyimides A can make the cementability polyimide film by said method.The cementability polyimide film can be by heat pressure adhesive with bonding by sticky object.Such as, can be with this cementability polyimide film and metal forming with the bonding flexible metal foil adhered laminate of making of continuous hot-press such as backer roll.The cementability polyimide film can also be clipped between semiconductor element and the support material and make it bonding by heat pressure adhesive.
Preferred 200～400 ℃ of heat pressure adhesive temperature, more preferably 250～350 ℃.Preferred 0.1～the 200kgf/cm of institute's plus-pressure
2, more preferably 1～100kgf/cm
2Also can under reduced pressure, carry out heat pressure adhesive in order to remove the gentle bubble that desolvates.Bonding agent of the application of the invention and cementability polyimide film can reach very good adhesive strength by the heat pressure adhesive under the above-mentioned condition.
Specify the present invention by the following examples.But the present invention is not subjected to any restriction of these embodiment.
Carry out as follows by the polyimide film of embodiment and reference examples gained and the evaluation of adhesive strength thereof.
(1) dielectric constant, the dielectric loss tangent
Use (strain) Northeast electronic application exploitation (Kanto ElectronicsApplication ﹠amp of Co., Ltd.; Development Inc.) the dielectric constant dielectric loss tangent determinator (CP431/461/501//531) of Sheng Chaning is measured dielectric constant, dielectric loss tangent by the cavity perturbation method.
(2) glass transition temperature
The differential scanning calorimeter device (DSC-50) that uses Shimadzu Seisakusho Ltd. (Shimadzu Corporation) to produce is to carry out DSC under the condition of 10 ℃/min to measure at programming rate, tries to achieve glass transition temperature.
(3) the anti-shearing resistance bonding strength of opening
According to JIS K 6848 and JIS K 6850, measure the anti-shearing resistance bonding strength of opening.
(4) adhesive strength
According to JIS C 6481, measure adhesive strength.
Reference example
1,2,4,5-cyclohexane tetracarboxylic dianhydride's is synthetic
With 552g PMA, 200g on active carbon carrier band the catalyst of rhodium (N.E.Chemcat Corporation manufacturing) and 1656g water add in the autoclave of the anti-corrosion Langaloy manufacturing of haas troy (HC22) of internal volume 5L, stir down with the gas in the nitrogen replacement reactor.Use the nitrogen in the hydrogen exchange reactor then, make the Hydrogen Vapor Pressure in the reactor reach 5.0MPa, be warming up to 60 ℃.Under the condition that keeps the 5.0MPa Hydrogen Vapor Pressure, make it to react 2 hours.With the hydrogen in the nitrogen replacement reactor, from autoclave, discharge reactant liquor, filter this reactant liquor separating catalyst while hot.With the moisture content in the rotary evaporator vapourisation under reduced pressure reactant liquor, concentrated, separated out crystallization.With the crystallization Separation of Solid and Liquid of separating out, obtained 481g (yield 85.0%) 1,2,4 after the drying, 5-cyclohexane tetrabasic carboxylic acid under the room temperature.
Then, with obtain 1,2,4,5-cyclohexane tetracid acid 450g adds 5 liters of glass together with acetic anhydride 4000g and separates flask (having the Di Muluo reflux condensing tube), while stirring with the reaction vessel nitrogen replacement.Under blanket of nitrogen, be warming up to the reflux temperature of solvent, made solvent refluxing 10 minutes.Be cooled to room temperature while stirring, crystallization is separated out.The crystallization of separating out is Separation of Solid and Liquid at room temperature, has obtained primary crystal after the drying.To separate mother liquor again and under reduced pressure, concentrate, separate out crystallization with rotary evaporator.Separation of Solid and Liquid is carried out in this crystallization, obtain secondary crystallization after the drying.To obtain 1,2,4,5-cyclohexane tetracid acid dianhydride 375g (yield of acid anhydridesization is 96.6%) after primary crystal and the secondary crystallization merging.
Embodiment 1
In 5 mouthfuls of flasks of the 500mL of the dropping funel that has thermometer, blender, nitrogen ingress pipe, band side pipe, Dean-Stark trap, condenser pipe, nitrogen current is following to add 4,4 '-diamino-diphenyl ether 10.0g (0.05 mole) and make its dissolving as the N-N-methyl-2-2-pyrrolidone N-85g of solvent, then at room temperature with in the reference example synthetic 1,2,4,5-cyclohexane tetracid acid dianhydride 11.2g (0.05 mole) solid drops into 1 hour time gradation, at room temperature stirs 2 hours.Then add azeotropic dehydration solvent xylene 30.0g, be warming up to 180 degree, reacted 3 hours, carry out refluxing xylene with Dean-Stark trap, azeotropic separation is removed the water of generation.After 3 hours, confirm that distillating of water finished after, be warming up to 190 ℃ of limits with 1 hour time limit and boil off dimethylbenzene, behind the recovery 29.0g, air cooling obtains the organic solvent solution of polyimides to 60 ℃ of internal temperatures.The solution that obtains is applied on the glass plate, and heating evaporation is removed organic solvent on 90 ℃ heating plate, then it is peeled off from glass plate, obtains independent film.This independent film fixedly is placed in the air drier with stainless steel stationary fixture and heated 2 hours under 220 ℃, and further with solvent evaporation, the thickness that has obtained the flexibility of Sandy is the film of 100 μ m.Measure the IR spectrum of this film, found that 1772,1700 (cm at v (C=O)
-1) locate the characteristic absorption of imide ring, be accredited as polyimides with repetitive shown in the following structural formula II.
The glass transition temperature of the film that obtains, dielectric constant, dielectric loss tangent are shown in table 1,2.
The organic solvent solution of the polyimides that obtains is applied to commercially available steel plate (cold-rolled steel sheet with scraper, JIS K6848,1.6 on * 25 * 100mm), make smearing thickness reach 1000 μ m, drying is 1 hour on 90 ℃ heating plate, further place air drier to descend dry 1 hour at 220 ℃ then, making it form thickness is the adhesive linkage of 100 μ m.This piece is had the steel plate of adhesive linkage and the sheet pack of same specification, is that 330 ℃ hot press carries out 30 minutes heat pressure adhesives by design temperature.The anti-shearing resistance bonding strength of opening when room temperature and 200 ℃ is as shown in table 1.The result shows that adhesive property is good.
Embodiment 2
The polyimide solution that is obtained by embodiment 1 is applied on the glass plate, and heating made solvent evaporation in 1 hour on 90 ℃ heating plate, stripped down from glass plate then and obtained independent film.This independent film is fixed on the stationary fixture of stainless steel the back in air drier 220 ℃ down heating solvent was further evaporated in 2 hours, obtain the cementability polyimide film of thickness 80 μ m of the flexibility of Sandy.Then, (cold-rolled steel sheet, JIS K6848 in the middle of 1.6 * 25 * 100mm), are that 330 ℃ hot press carries out 30 minutes heat pressure adhesives by design temperature the cementability polyimide film that obtains to be clipped in 2 commercially available steel plates.The anti-shearing resistance bonding strength of opening when room temperature and 200 ℃ is as shown in table 1.The result shows that adhesive property is good.
Reference examples 1
With 5 mouthfuls of flasks of the same 500ml of embodiment in add 4,4 '-diamino-diphenyl ether 10.0g (0.05 mole) and make its dissolving as the dimethylacetylamide 85.0g of organic solvent, under nitrogen current, under the room temperature pyromellitic acid dianhydride 10.9g (0.05 mole) is added with 1 hour with solid then, add under the room temperature of back and stirred 3 hours, obtain polyamic acid solution.
The polyamic acid solution that obtains is applied on the glass plate, and drying is 1 hour on 50 ℃ heating plate, peels off from glass plate then and obtains independent film.This independent film is fixed on the stationary fixture of stainless steel and places air drier, drying is 3 hours under 100 ℃, drying is 3 hours under 200 ℃, drying is 2 hours under 250 ℃, drying is 1 hour under 300 ℃, again 400 ℃ dry 1 hour down, obtain the film of thickness 50 μ m of the flexibility of brown.Glass transition temperature, the dielectric constant of the film that obtains are as shown in table 1.
With the polyamic acid bonding agent with scraper be applied to commercially available steel plate (cold-rolled steel sheet, JIS K6848 is on 1.6 * 25 * 100mm), make smearing thickness reach 500 μ m, drying is 1 hour on 50 ℃ heating plate, places air drier then, and drying is 3 hours under 100 ℃, drying is 3 hours under 200 ℃, 250 ℃ dry 2 hours down, 300 ℃ dry 1 hour down, again 400 ℃ dry 3 hours down, carry out imidizate and handle, make it to form the adhesive linkage that thickness is 50 μ m.This steel plate that has an adhesive linkage and the sheet pack of same specification are in the same place, and are that 30 minutes heat pressure adhesives are carried out in 350 ℃ hot pressing by design temperature.The anti-shearing resistance adhesive strength of opening under the room temperature is as shown in table 1.The result shows the adhesive strength deficiency.
Table 1
| Embodiment 1 | Embodiment 2 | Reference examples 1 | |
| Polyimides tetrabasic carboxylic acid composition two amine components | CTDA ODA | CTDA 0DA | PMDA 0DA |
| Glass transition temperature (℃) | 315 | 315 | >400 |
| Dielectric constant during 10Ghz | 3.02 | 3.02 | 3.2 |
| Pressure condition (min/ ℃) | 30/330 | 30/330 | 30/350 |
| The anti-shearing resistance adhesive strength (kgf/cm that opens 2) 200 ℃ of room temperatures | 230 175 | 243 154 | <20 --- |
Used steel plate: cold-rolled steel sheet, JIS K6848,1.6 * 25 * 100mm
CTDA:1,2,4,5-cyclohexane tetracarboxylic dianhydride
PMDA: pyromellitic acid dianhydride
ODA:4,4 '-diamino-diphenyl ether
Table 2
Embodiment 3
In 5 mouthfuls of flasks of similarly to Example 1 500ml, add in the reference example synthetic 1,2,4,5-cyclohexane tetracarboxylic dianhydride 11.2g (0.05 mole) and make its dissolving as the N-dimethyl-2-Pyrrolidone 40.0g of solvent, with 4, the solution that 4 '-diamino-dicyclohexyl methane 10.5g (0.05 mole) is dissolved in the formation of 45.0g dimethylacetylamide drips with 2 hours by dropping funel under the room temperature.Be warming up to 90 ℃ after dropwising, stirred 1 hour.Then add azeotropic dehydration solvent xylene 30.0g, be warming up to 180 ℃ again, reacted 3 hours, with the Dean-Stark trap dimethylbenzene that refluxes, the water that azeotropic separation goes out to generate.Confirm after 3 hours that moisture steams end, boil off dimethylbenzene, reclaim and obtain 30.0g while be warming up to 190 ℃ with 1 hour time.Air cooling to internal temperature becomes 60 ℃ then, obtains the organic solvent solution of polyimides.The solution that obtains is applied on the glass plate, and heating made organic solvent evaporation in 1 hour on 90 ℃ heating plate, peeled off from glass plate then and obtained independent film.This independent film is fixed on places air drier on the stainless steel stationary fixture, just obtained the film of the thickness 100 μ m of water white flexibility at 220 ℃ of following further evaporation organic solvents of heating 2 hours.Measure the IR spectrum of this film, the result shows 1754, the 1691 (cm at v (C=O)
-1) locate the characteristic absorption of imide ring, through being accredited as polyimides with the repetitive shown in the formula III.
The glass transition temperature of the film that obtains, dielectric constant, dielectric loss tangent are as shown in table 3.
The polyimides organic solvent solution that obtains is applied to the electrolytic copper foil that thickness is 18 μ m ((the Mitsui Mining ﹠amp of Mitsu Mining ﹠ Smelting Co., Ltd with scraper; Smelting Co. Ltd.) produces 3EC-VLP) on, smearing thickness is 200 μ m, drying is 1 hour on 90 ℃ heating plate, places air drier to descend dry 1 hour at 220 ℃ again, makes it to form the adhesive linkage that thickness is 20 μ m.This is had the Copper Foil of adhesive linkage and commercially available polyimide film (Du-Pont-TorayCo., Ltd. produce Kapton 100H, thickness is 25 μ m) stack, the hot press by 280 ℃ of design temperatures carries out 30 minutes heat pressure adhesives, has just obtained the copper adhered laminate.Adhesive strength at room temperature is as shown in table 3.The copper adhered laminate has enough flexible, even its bending can not peeled off yet, has good cementability.
Embodiment 4
The polyimides organic solvent solution that obtains among the embodiment 3 is applied on the glass plate, and heating made organic solvent evaporation in 1 hour on 90 ℃ heating plate, peeled off from glass plate then and obtained independent film.This independent film is fixed on the stainless steel stationary fixture, places air drier to heat down and made organic solvent evaporation in 2 hours, obtain the film of the thickness 30 μ m of water white flexibility at 220 ℃.Then, in the middle of the polyimide film that the obtains electrolytic copper foil (3EC-VLP) that to be clipped in 2 thickness be 18 μ m, the hot press by 280 ℃ of design temperatures carries out 30 minutes heat pressure adhesives, obtains the duplexer of two sides copper-surfaced.Adhesive strength under the room temperature is as shown in table 3.The copper adhered laminate has enough flexible, even its bending can not peeled off yet, has good cementability.
Reference examples 2
The polyamic acid solution that obtains in the reference examples 1 is applied on the glass plate, and heating made organic solvent evaporation in 1 hour on 90 ℃ heating plate, peeled off from glass plate then and obtained independent film.This independent film is fixed on the stainless steel stationary fixture, place air drier to heat 2 hours down at 100 ℃, heated 3 hours down at 200 ℃, heated 2 hours down at 250 ℃, heated 1 hour down at 300 ℃, heated 1 hour down at 400 ℃, make solvent evaporation, the thickness that has obtained the flexibility of brown is the polyimide film of 30 μ m.In the middle of the polyimide film that the obtains electrolytic copper foil (3EC-VLP) that to be clipped in 2 thickness be 18 μ m, the hot press by 330 ℃ of design temperatures carries out 30 minutes heat pressure adhesives, obtains the duplexer of two sides copper-surfaced.Adhesive strength under the room temperature is as shown in table 3.
Table 3
| Embodiment 3 | Embodiment 4 | Reference examples 2 | |
| Polyimides tetrabasic carboxylic acid composition two amine components | CTDA DCHM | CTDA DCHM | PMDA 0DA |
| Glass transition temperature (℃) | 261 | 261 | >400 |
| Dielectric constant during 10GHz | 2.80 | 2.80 | 3.2 |
| Pressure condition (min/ ℃) | 30/280 | 30/280 | 30/350 |
| Adhesive strength (kgf/cm 2) | 1.50 | 1.40 | <0.5 |
The Copper Foil that uses: Mitsu Mining ﹠ Smelting Co., Ltd produces, 3EC-VLP (thickness is 18 μ m)
The polyimide film that uses: Du-Pont-Toray company produces, Kapton 100H (thickness is 25 μ m)
CTDA:1,2,4,5-cyclohexane tetracarboxylic dianhydride
PMDA: pyromellitic acid dianhydride
ODA:4,4 '-diamino-diphenyl ether
DCHM:4,4 '-diamino-dicyclohexyl methane
Bonding agent of the present invention and cementability polyimide film have the dielectric property under good cementability, thermal endurance, the flexible and high frequency, bonding very useful to electric material and other industrial materials.
Claims (10)
1. the bonding agent that contains the organic solvent solution formation of polyimides with repetitive shown in the general formula I:
The 4 valency groups that R comes for being derived by cyclohexane, Φ are that carbon number is the group that 2～39 divalent fatty group, alcyl, aromatic radical or they combine, have on the main chain of Φ or do not have to be selected from-O-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-,-OSi (CH
3)
2-,-C
2H
4O-,-at least one group among the S-.
2. the bonding agent of putting down in writing as claim 1, the glass transition temperature that it is characterized in that above-mentioned polyimides is below 350 ℃.
3. as claim 1 or 2 bonding agents of being put down in writing, it is characterized in that the dielectric constant of above-mentioned polyimides when 10GHz is below 3.2.
4. as claim 1 or 2 bonding agents of being put down in writing, it is characterized in that above-mentioned organic solvent is to be selected from N-N-methyl-2-2-pyrrolidone N-, N, N-dimethylacetylamide, N, at least a solvent in dinethylformamide, methyl-sulfoxide, hempa acid amide, sulfolane, parachlorophenol, metacresol, gamma-butyrolacton, propylene carbonate, dioxane, the 2-chloro-4-hydroxy-methylbenzene.
5. as claim 1 or 2 bonding agents of being put down in writing, the concentration that it is characterized in that the above-mentioned polyimides in the above-mentioned organic solvent solution is 1～50 weight %.
6. as claim 1 or 2 bonding agents of being put down in writing, it is characterized in that becoming film like by evaporating above-mentioned organic solvent.
7. the cementability polyimide film that has the polyimides formation of repetitive shown in the general formula I:
The 4 valency groups that R comes for being derived by cyclohexane, Φ are that carbon number is the group that 2～39 divalent fatty group, alcyl, aromatic radical or they combine, have on the main chain of Φ or do not have to be selected from-O-,-SO
2-,-CO-,-CH
2-,-C (CH
3)
2-,-OSi (CH
3)
2-,-C
2H
4O-,-at least one group among the S-.
8. the cementability polyimide film of putting down in writing as claim 7, the glass transition temperature that it is characterized in that above-mentioned polyimides is below 350 ℃.
9. the cementability polyimide film of being put down in writing as claim 7 or 8 is characterized in that the dielectric constant of above-mentioned polyimides when 10GHz is below 3.2.
10. the cementability polyimide film of being put down in writing as claim 7 or 8 is characterized in that thickness is 1～600 μ m.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP131722/2003 | 2003-05-09 | ||
| JP2003131722 | 2003-05-09 | ||
| JP133357/2003 | 2003-05-12 | ||
| JP2003133357 | 2003-05-12 |
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| CN100512602C true CN100512602C (en) | 2009-07-08 |
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|---|---|---|---|
| CNB2004100421473A Expired - Fee Related CN100512602C (en) | 2003-05-09 | 2004-05-09 | Adhesive and adhesive film |
Country Status (3)
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|---|---|
| KR (1) | KR101056555B1 (en) |
| CN (1) | CN100512602C (en) |
| TW (1) | TWI341859B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MXPA06010596A (en) * | 2005-12-23 | 2007-06-22 | 3M Innovative Properties Co | High temperature heat resistant adhesive tape, with low electrostatic generation, made with a polyetherimide polymer. |
| EP2738199B1 (en) * | 2012-02-08 | 2015-09-16 | Mitsubishi Gas Chemical Company, Inc. | Crystalline thermoplastic polyimide resin |
| CN108327377B (en) * | 2018-03-13 | 2023-05-23 | 广西师范大学 | A preparation device for polyimide film or polyimide copper clad laminate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094862A (en) * | 1974-03-05 | 1978-06-13 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Process for preparing thermoplastic aromatic polyimides |
| US4915983A (en) * | 1985-06-10 | 1990-04-10 | The Foxboro Company | Multilayer circuit board fabrication process |
| CN1406262A (en) * | 2000-02-01 | 2003-03-26 | 新日铁化学株式会社 | Adhesive polyimide resin and adhesive laminate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR910000867B1 (en) * | 1987-01-27 | 1991-02-11 | 미쯔이도오 아쯔 가가꾸 가부시기가이샤 | Manufacturing method and bonding method of polyimide for heat resistant adhesive |
| JP4147639B2 (en) * | 1998-09-29 | 2008-09-10 | 宇部興産株式会社 | Flexible metal foil laminate |
| KR100917101B1 (en) * | 2000-08-04 | 2009-09-15 | 도요 보세키 가부시키가이샤 | Flexible metal laminate and production method thereof |
| JP4491986B2 (en) * | 2001-03-29 | 2010-06-30 | 宇部興産株式会社 | Surface treatment method and polyimide film having metal thin film |
-
2004
- 2004-05-05 TW TW093112604A patent/TWI341859B/en not_active IP Right Cessation
- 2004-05-07 KR KR1020040032370A patent/KR101056555B1/en not_active Expired - Fee Related
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094862A (en) * | 1974-03-05 | 1978-06-13 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Process for preparing thermoplastic aromatic polyimides |
| US4915983A (en) * | 1985-06-10 | 1990-04-10 | The Foxboro Company | Multilayer circuit board fabrication process |
| CN1406262A (en) * | 2000-02-01 | 2003-03-26 | 新日铁化学株式会社 | Adhesive polyimide resin and adhesive laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200502347A (en) | 2005-01-16 |
| KR101056555B1 (en) | 2011-08-11 |
| CN1551715A (en) | 2004-12-01 |
| KR20040095739A (en) | 2004-11-15 |
| TWI341859B (en) | 2011-05-11 |
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