CN1188501A - Adhesive compositions, bonding films made therefrom and processes for making bonding films - Google Patents
Adhesive compositions, bonding films made therefrom and processes for making bonding films Download PDFInfo
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- CN1188501A CN1188501A CN96194955A CN96194955A CN1188501A CN 1188501 A CN1188501 A CN 1188501A CN 96194955 A CN96194955 A CN 96194955A CN 96194955 A CN96194955 A CN 96194955A CN 1188501 A CN1188501 A CN 1188501A
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Abstract
A photostable adhesive composition comprises: a) an aromatic polyepoxide; b) a heat activated curative for polyepoxide; c) a thermoplastic polymer; d) a polyfunction (meth)acrylate; and e) optionally, a bireactive compound that contains at least one (meth)acrylate group and at least one group that is reactive with aromatic polyepoxide. The adhesive compositions can be used to prepare adhesive bonding films in a process that uses electron beam irradiation.
Description
Invention field
The present invention relates generally to binder composition, with its bonding film that makes with prepare the method for bonding film.More specifically, the present invention relates to contain Resins, epoxy, contain the resin of (methyl) acrylate and the binder composition of thermoplastic polymer, and make the method for bonding film by electron beam irradiation with it.
Description of related art
When making member and veneer sheet, often use solid-state continuous bonding film that 2 substrates are bonded together.Such bonding film usually is used for electronics, automobile and Aerobiz.For example, by the tackiness agent bonding film being placed in the middle of 2 copper facing substrates that contain etched circuit, heating is solidified binder film then, can make stacked wiring board.
The tackiness agent bonding film that is used to make member and veneer sheet preferably should have multiple performance.For example, they should be easy to use.In other words, they should be able to take off from interim carrier (as release liner), and place on the substrate and fold does not take place, tear or nonvolatil stretching.
The tackiness agent bonding film also should show controlled flowability (promptly to a certain degree but not over-drastic adhesive flow) in curing process.To a certain degree adhesive flow needs in curing process, so that wetting substrate surface and form the even bonding coat with homogeneous bond strength.Yet undue adhesive flow can cause tackiness agent to ooze out the substrate edge in curing process, forms uneven bonding coat, space and causes bond strength inconsistent.In addition, after thermofixation, tackiness agent bonding film reply substrate has good binding property.At least use for some, the tackiness agent bonding film after the thermofixation also should have high glass-transition temperature, with the thermostability that increases veneer sheet and reduce thermal expansion.This is particularly advantageous performance in the welding (being wave soldering) of subsequently high-temperature process such as circuit card.
Accept face in order to enlarge coml, also should be easy to use and handle from its binder composition of producing bonding film.For example, binder composition is upright certain viscosity, thereby can be mixed and applied under very not high temperature, thereby avoids that any hot activation solidifying agent reacts too early in the tackiness agent.
Can the polymeric material when many binder compositions contain heat-setting material simultaneously and are exposed to actinic radiation (as visible light or ultraviolet ray).These tackiness agents need be stored under " safety light " condition.Thereby to have the binder composition that does not need lucifuge or keep away ultraviolet ray storage be favourable.
But containing the resin of radiation polymerization and the tackiness agent bonding film of heat-setting resin simultaneously is disclosed already.For example U.S. Patent No. 4,552,604 (Green) have described a kind of method that two surfaces is bonded together with fluid composition, said composition contains epoxide resin and a kind of compound, this compound can because of be exposed to actinic radiation (the especially wavelength of 200-600 nanometer) photopolymerization become solid-state basically continuous film not can with film generation heat cross-linking.General adopt 10: 1 to 1: 10 epoxide resin, form gratifying film and solidified adhesion results satisfactorily the mol ratio of photopolymerization compound.Should use the photopolymerization catalyzer.Can be by applying heat and pressure (if desired), this film can be bonded together the surface.
U.S. Patent No. 4,612,209 (people such as Forgo) disclose use actinic radiation (the especially wavelength of 200-600 nanometer) and have prepared the heat-setting tackiness agent bonding film with different clinging powers.Its tackiness agent is the mixture of following component: contain at least one CH
2The compound of the photopolymerization of=C (R) COO-base (wherein R is hydrogen or methyl), do not contain photopolymerizable group, heat-setting epoxide resin, what be used for Resins, epoxy can heat activated solidifying agent, setting accelerator and the photopolymerization catalyzer that is used for the photopolymerization compound.
U.S. Patent No. 5,068,088 (people such as Kitano) discloses a kind of acrylate/composition epoxy resin, can form pressure-sensitive thermosetting adhesive when it is exposed to ultraviolet radiation.This tackiness agent contains that the prepolymerization slurry of the 30-80 weight % photopolymerization of having an appointment or monomer slurry (containing acrylate and monomer copolymerizable, middle polarity), about 20-60 weight % do not contain the Resins, epoxy of photopolymerizable group or epoxy resin composition, about 0.5-10 weight % is used for the hot activation stiffening agent of Resins, epoxy, about 0.01-5% light trigger and about 0-5% photocrosslinking agent.This tackiness agent can be used for unit construction be bonded in the metallic surface, perhaps be used for the closed metal crack.
Described a kind of resin combination in Japanese patent application publication No. No.61/14274 (people such as Ando), it contains low-molecular-weight urethane-acrylate (urethane-acrylate), Resins, epoxy, acrylate or methacrylate monomer and epoxy hardener.This resin combination forms thermosetting adhesive by electrolysis irradiation (as electron beam, gamma-rays or X-ray), it is reported to have caused urethane acrylate and acrylate monomer generation polymerization and be cross-linked with each other.
Japanese patent application publication No. No.1/234417 (people such as Yamamoto) has described a kind of available electron bundle irradiation and has carried out crosslinked composition epoxy resin.This composition contains a) Resins, epoxy, b) has the Resins, epoxy of at least one epoxy group(ing) and at least one unsaturated double-bond at an intramolecularly, and c) be used for the thermal curing agents of Resins, epoxy, wherein component (a) and weight ratio (b) are 0.95/0.05 to 0.10/0.90.Use electron beam irradiation, said composition can be earlier forms case-hardened state by two keys are crosslinked.Then can further thermofixation in second step.It is reported, if do not use enough components (b), so crosslinked just seldom and also the surface can not fully harden.
The method of a kind of production prepreg (pre-preg) is disclosed in Japanese patent application publication No. No.58/19332 (people such as Takita).Flood the enhanced base material with the resin solution that contains 100 parts by weight Resins, epoxy, 2-150 parts by weight epoxy curing agent and 20-150 parts by weight acrylate monomer.Carry out irradiation with electronics beam line, make and have only acrylate monomer to be cured.Thereby form the prepreg that does not have viscosity to be convenient to operate.It is reported, just insufficient by the curing that electron beam irradiation carries out when the consumption of the component that contains acrylate is lower than the consumption of being advised, thereby can make still toughness of surface.
Therefore still need a kind of binder composition, it can provide has bonding film part and that preferably have whole following performances: easy handling, in curing process controlled resin flows and after thermofixation high glass transition temperature.If not lucifuge or the ultraviolet ray of when storage, and if can under the temperature that can not cause hot activation catalyzer premature reaction, process, the purposes of this binder composition also can further be expanded so.
Summary of the invention
In an example, the invention provides a kind of binder composition, it contains:
A) aromatic polyepoxide;
B) the hot activation solidifying agent of polyepoxide;
C) thermoplastic polymer;
D) polyfunctional (methyl) acrylate; With
E) compound of Ren Xuan double reactive, it contain at least one (methyl) acrylate group and at least one can with the group (as hydroxyl, carboxyl, amine or 1,2-epoxide) of aromatic polyepoxide reaction.
This binder composition is that light is stable, and they do not rely on actinic radiation to come polymerization.Therefore, they do not need photocatalyst, need not store (as being stored in the light tight or ultraviolet container) under the condition of " safe light " yet.Preferable binder composition of the present invention also can be operated and process easily, because they can be mixed, (as be lower than about 120 ℃ temperature in the temperature that can not cause polyepoxide solidifying agent premature reaction then, more preferably be lower than about 90 ℃, best between about room temperature to 60 ℃) under apply.
Can use various aromatic polyepoxide, but preferably comprise many glycidyl ethers and 4,4 of phenolic varnish '-diglycidyl ether of dihydroxyl phenylbenzene dimethylmethane.Similarly, can adopt various hot activation solidifying agent, but preferably aromatic polyamine class such as fluorenediamine compounds.
Be used for the mixture that thermoplastic polymer of the present invention comprises polysulfones, poly-(methyl methacrylate), phenoxy group polymkeric substance, polycarbonate and these materials.Preferably, the second-order transition temperature of thermoplastic polymer is about 90-200 ℃, and number-average molecular weight is about 10,000-100,000.For per 100 parts by weight aromatic polyepoxides, thermoplastic polymer is preferably about 20-40 parts by weight, is more preferably about the 20-30 parts by weight.
Polyfunctional (methyl) the preferably sufficient aromatics two of acrylate (methyl) acrylate, and for per 100 parts by weight aromatic polyepoxides, account for about 5-20 parts by weight usually.For per 100 parts by weight aromatic polyepoxides, very favorable but can choose the double reactive compound that contains wantonly and be generally about 1-15 parts by weight.For per 100 parts by weight aromatic polyepoxides, the merging quantity of the compound of polyfunctional (methyl) acrylate and double reactive (if the latter exists) is preferably about 10-25 parts by weight (being more preferably about the 15-20 parts by weight).
In case be exposed to electron beam irradiation, just polymerization and crosslinked of multifunctional (methyl) acrylate and double reactive compound (if existence), form poly-(methyl) acrylate net, and polymerization does not take place in the hot activation solidifying agent of aromatic polyepoxide, polyepoxide and the thermoplastic polymer that preferably contains.As a result, this binder composition provides a kind of heat-setting tackiness agent bonding film, and this film contains:
A) heat-setting aromatic polyepoxide;
B) the hot activation solidifying agent of polyepoxide;
C) thermoplastic polymer; With
D) (methyl) acrylic ester polymer net, it is the electron beam irradiation polymerisate of following component:
1) polyfunctional (methyl) acrylate; With
2) compound of Ren Xuan double reactive, it contain at least one (methyl) acrylate group and at least one can with the group of aromatic polyepoxide reaction.
The heat-setting tackiness agent bonding film easy handling that the present invention is preferable, and may command flows in curing process.After thermofixation, the preferable tackiness agent bonding film of the present invention has good binding property and second-order transition temperature height for its substrate that applies.
The invention still further relates to a kind of method for preparing the tackiness agent bonding film.The method comprising the steps of:
A) provide aforesaid binder composition;
B) go up the formation adhesive composition layer at area supported (as nonvolatil backing or provisional carrier such as release liner); With
C) adhesive composition layer is exposed to electron beam irradiation,, does not still cause the reaction of hot activation solidifying agent or aromatic polyepoxide with polymerization multifunctional (methyl) acrylate and optional double reactive compound (if existence).
Heat-setting tackiness agent bonding film has just formed.By making under the aromatic polyepoxide solidified temperature being enough to, heat heat-setting tackiness agent bonding film for some time, just can obtain (being thermoset) tackiness agent bonding film of thermofixation.
The detailed description of preferred example
On the one hand, the present invention relates to contain the binder composition of following component, more preferably said composition is made of following component basically:
A) aromatic polyepoxide;
B) the hot activation solidifying agent of polyepoxide (being called as " heat activated polyepoxide solidifying agent " or " polyepoxide solidifying agent " in this article sometimes);
C) thermoplastic polymer;
D) polyfunctional (methyl) acrylate; With
E) randomly, a kind of compound, this compound contain at least one (methyl) acrylate group and at least one can with the group (this compound is called as " double reactive compound " sometimes in this article) of aromatic polyepoxide reaction.
The invention still further relates to the heat-setting tackiness agent bonding film that makes with this binder composition, and the method for preparing this film.In brief, for example heat-setting tackiness agent bonding film can form like this: in area supported such as permanent backing or the last adhesive composition layer that forms of provisional carrier (as release liner), then this binder layer is exposed to electron beam irradiation.(word " bonding film ", " tackiness agent bonding film " and " heat-setting tackiness agent bonding film " are used with the free burial ground for the destitute in this article, all refer to after forming film and being exposed to electron beam irradiation but at film by the binder composition before the thermofixation.)。
The invention still further relates to the various goods that make with this binder composition and this tackiness agent bonding film.For example, in making veneer sheet, the tackiness agent bonding film is placed in the middle of two substrates, changed into thermosetting material (i.e. the crosslinked polymeric web that can not flow or melt) by thermosetting then.(word " final tackiness agent bonding film " and " the tackiness agent bonding film of thermofixation " are used with the free burial ground for the destitute in this article, all refer to be changed into thermosetting material tackiness agent bonding film afterwards by thermosetting.)
Advantageously, preferred adhesive composition easy handling of the present invention and processing.These compositions have certain viscosity, and it can mixedly be applied under the temperature that can not cause polyepoxide solidifying agent premature reaction then.Because the material that the present composition contains is polymerization and do not rely on photopolymerization reaction when being exposed to electron beam irradiation,, this binder composition need under " safe light " condition, not store this advantage so having.
The preferred heat-setting tackiness agent bonding film of the present invention is easy handling also.These bonding films can take off from interim carrier, place then on the substrate and fold can not take place, tear or nonvolatil stretching (promptly not having the change of nonvolatil size or thickness aspect).Tackiness agent bonding film with preferred adhesive composition of the present invention makes also has controllable adhesive flow in curing process.In these bonding films, the wetting substrate surface thereby tackiness agent can flow fully forms the even bonding coat with homogeneous bond strength.Yet adhesive flow can not be excessive in curing process.For example when making veneer sheet, tackiness agent can not ooze out the edge of substrate, also can not form uneven bonding coat, space or inconsistent bond strength.After thermofixation, tackiness agent bonding film of the present invention has good binding property to its substrate that applies.The tackiness agent bonding film of preferred thermofixation has (at least 120 ℃ usually of high glass-transition temperatures, preferably at least 140 ℃, more preferably at least 150 ℃, at least 160 ℃ best), structural articles and veneer sheet that this characteristic can be used for providing heat-staple, thermal expansivity is low.
" polyepoxide (polyepoxide) " refers to contain at least 21, the compound of 2-epoxy group(ing), and 1, the 2-epoxy group(ing) is promptly descended the group of array structure:
Aromatic polyepoxide is favourable, because they can give the tackiness agent bonding film hot properties (as high glass-transition temperature) of thermofixation, but also can give structure properties.Can use the mixture of different aromatic polyepoxides.
The aromatic polyepoxide that is applicable to binder composition of the present invention and tackiness agent bonding film comprises: many glycidyl ethers of following polyphenol, as pyrocatechol, Resorcinol, Resorcinol, 4,4 '-the dihydroxyl ditan, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenylmethane, 4,4 '-dihydroxyl diphenylmethyl methylmethane, 4,4 '-dihydroxyl phenylbenzene dimethylmethane, 4,4 '-dihydroxy-phenyl-cyclohexane, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl propane, 4,4 '-dihydroxy-diphenyl sulfone, three-(4-hydroxy phenyl) methane, 9,9 '-neighbour of two (4-hydroxy phenyl) fluorenes and these compounds replaces (ortho-substituted) analogue (as in U.S. Patent No. 4,707, and many glycidyl ethers of the halogenation of described polyphenol (as chlorination and bromination) product disclosed kind in 534).
Other suitable aromatic polyepoxides comprise many Racemic glycidols radical derivative (being glycidyl group amine) of aromatic amine, and it can obtain by the reaction of aromatic amine and epihalohydrin.The example of this glycidyl group amine comprises: N, the N-diglycidylaniline, N, N '-dimethyl-N, N '-diglycidyl-4,4 '-diaminodiphenyl-methane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl naphthylamines (name that Chemical Abstracts 9th Coll.8505F (1982-1979) provides is called N-1-naphthyl-N-(oxiranylmethyl radical) oxyethane methane amine), N, N, N ', N '-four glycidyl group-1, two [(α-4-the aminophenyl)-Alpha-Methyl ethyl] benzene of 4-, and N, N, N ', N '-four glycidyl group-1, two [the α-(4-amino-3,5-3,5-dimethylphenyl)-[Alpha-Methyl ethyl] benzene of 4-.U.S. Patent No. 2,951, described in 825, many Racemic glycidols radical derivative of aromatic amine phenol (as glycidyl-amino-glycidyl oxygen base benzene) also is suitable.An example of these compounds is N, N-diglycidyl-4-glycidyl oxygen base aniline.
Aromatic multi-carboxy acid's poly glycidyl ester, for example the 2-glycidyl ester of phthalic acid, m-phthalic acid or terephthalic acid also can use.
Preferably, aromatic polyepoxide be selected from down the group in a kind of: many glycidyl ethers of phenolic varnish (being monobasic or multi-phenol and aldehyde (especially formaldehyde) reaction product in the presence of acid catalyst); Or 4,4 '-diglycidyl ether of dihydroxyl phenylbenzene dimethylmethane.
The example that can be used for the commercially available aromatic polyepoxide of binder composition of the present invention and tackiness agent bonding film has: MY
TM-720 (Ciba-Geigy, Inc., Hawthorne, NY); ERL-0510 (Ciba-Geigy, Inc.); From Shell Chemical Co., Houston, the EPON of TX
TMSeries material (as EPON HPT-1071, EPON HPT-1072, EPON HPT-1079 and EPON 828); Dow Chemical Company, Midland, the D.E.R. of MI
TM, D.E.N.
TMAnd QUATREX
TMFamily's material (as D.E.R.332, D.E.R.361, D.E.N.438 and QUATREX 1010).
Although can use solid-state aromatic polyepoxide resin, but preferably polyepoxide or polyepoxide mixture at room temperature are essentially liquid, the viscosity that this means polyepoxide (or polyepoxide mixture) allows it at room temperature or be heated to slightly under the temperature that can not cause polyepoxide solidifying agent premature reaction (as room temperature to about 120 ℃), mixed coating (as applying) then, liquid aromatic polyepoxide helps mixing and the application of adhesive composition under the low temperature that can not activate the polyepoxide solidifying agent.
Preferably, the average epoxy functional degree of aromatic polyepoxide (or polyepoxide mixture) is 2-4, and preferably average epoxy functional degree is 2-3.Help so both providing and to mix and to apply and the binder composition of hot activation solidifying agent premature reaction can not take place, help the final tackiness agent bonding film that provides full cross-linked again.The epoxy equivalent (weight) weight of aromatic polyepoxide (or polyepoxide mixture) is preferably about 80-200 gram/equivalent.This helps forming the binder composition that has the effective mixing of certain viscosity permission and apply, and the final tackiness agent bonding film with acceptable high glass-transition temperature.For the electronics industry purposes, best its contained ionic state of aromatic polyepoxide or the halid concentration of hydrolyzable are low, because these materials can cause corrosion phenomenon in the printed wiring veneer sheet of making.
Binder composition of the present invention also contains the hot activation solidifying agent of polyepoxide.This hot activation solidifying agent is dissolvable in water or is scattered in term in the binder composition " solidifying agent " and broadly uses, it comprises that not only routine is considered to the material of solidifying agent, but also comprise catalysis epoxide polymerization reaction material and can be simultaneously as the material of solidifying agent and catalyzer.Can use the mixture of different hot activation solidifying agent.The example that can be used for the hot activation solidifying agent of binder composition of the present invention and tackiness agent bonding film comprises polyprotonic acid and acid anhydrides thereof, as binary-, ternary-and polybasic carboxylic acid, the Succinic Acid, tartrate, Tetra hydro Phthalic anhydride, Succinic anhydried, maleic anhydride, NA acid anhydrides (nadicanhydride), the PMA that replace as oxalic acid, phthalic acid, terephthalic acid, Succinic Acid, alkyl; With the polymeric unsaturated acid, as contain the kind of at least 10 carbon atoms, such as dodecenedioic acid, 10,12-20 carbon diene bisgallic acids (eicosadiendioic acid) etc.
Other can be used for hot activation solidifying agent of the present invention and comprise: nitrogenous compound such as Dyhard RU 100, melamine, ureas and aliphatic amine are (as diethylenetriamine, Triethylenetetramine (TETA), cyclo-hexylamine, trolamine, piperidines, four hexyl piperamine, N, N-dibutyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1,2-diamino-2-methyl-propane, 2,3-diamino-2-methyl-butane, 2,3-diamino-2-methyl-pentane, 2,4-diamino-2,6-dimethyl-octane, dibutylamine and dioctylamine).
What also can be used as solidifying agent is the Lewis acid of chloride, the bromine and the fluorine of aluminium, boron, antimony and titanium, as aluminum chloride, alchlor, boron trifluoride, antimony pentafluoride, titanium tetrafluoride etc.Sometimes, these Lewis acid are protected the latent (latency) that contains the binder composition of Lewis acid with increase.Representational protected Lewis acid is BF
3-monoethylamine, and HSbF
5The adducts of X, wherein X be halogen atom ,-OH or-OR
1(R wherein
1Be the alcohol of aliphatic series or aromatics, the residue of aniline or derivatives thereof), as in U.S. Patent No. 4,503, the kind of describing in 211.Pyridine, benzyl dimethyl amine, benzyl amine and Diethyl Aniline also can be used as the hot activation solidifying agent.Some solidifying agent described herein more generally is to mix use with other solidifying agent, rather than uses separately.
Preferably, the hot activation solidifying agent is an aromatic polyamine, as adjacent-, between-, and p-phenylenediamine, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, sulfuration 4,4 '-diamino-diphenyl, 4,4 '-diamino-diphenyl ketone, 4,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 1, ammediol-two-(4-Aminobenzoate), 1, two [α-(4-the aminophenyl)-Alpha-Methyl ethyl] benzene of 4-, with 1, two [α-(4-amino-3,5-the 3,5-dimethylphenyl)-Alpha-Methyl ethyl] benzene of 4-, two α-(4-amino-3-aminomethyl phenyl) sulfone, 1,1 '-xenyl-3,3 '-dimethyl-4,4 '-diamines, 1,1 '-xenyl-3,3 '-dimethoxy-4 ', 4 '-diamines, and diaminonaphthalene.
Best as the hot activation solidifying agent be fluorenediamine, as 9,9 '-two (4-aminophenyl) fluorenes, 9,9 '-two (3-methyl-4-aminophenyl) fluorenes and 9,9 '-two (3-chloro-4-aminophenyl) fluorenes.
The example that can be used for commercially available hot activation solidifying agent of the present invention has EPON
TMHPT-1061 and EPON
TMHPT-1062 (all from Shell Chemical Co.), HT-9664 (Ciba Geigy, Inc.) and AMICURE
TMCG-1400 (Air Products, Pacific Anchor Chemical, Allentown, PA.).
The heat activated polyepoxide solidifying agent that is used for binder composition of the present invention and tackiness agent bonding film, when being exposed to electron beam irradiation, with the polyepoxide reaction, they do not suppress the polyreaction by the electron beam irradiation initiation better.Be used for preferred hot activation solidifying agent of the present invention and have the potential heat reactivity; In other words, their mainly reactions at high temperature (preferably at least 120 ℃, more preferably at least 130 ℃, at least 140 ℃ best).This can mix and apply binder composition easily under room temperature (about 20-22 ℃), perhaps can heat a little and do not activate under the condition of solidifying agent and carry out (promptly under the temperature that is lower than polyepoxide solidifying agent temperature of reaction).
For the electronics industry purposes, the polyepoxide solidifying agent does not preferably contain or only contains a spot of ionic state or hydrolyzable halogenide, because these materials can cause corrosion phenomenon in the printed wiring veneer sheet of making.
Binder composition of the present invention and tackiness agent bonding film also can contain thermoplastic polymer." thermoplasticity " can repeat noncrosslinking polymkeric substance softening and that formalize again when referring to apply heat and pressure.
Preferably, this thermoplastic polymer dissolved in the aromatic polyepoxide before being exposed to electron beam irradiation.The second-order transition temperature of thermoplastic polymer is preferably for about 90-200 ℃, thereby can promote it to have the excellent high-temperature performance during by thermofixation when binder composition, and then makes tackiness agent have better purposes, as is applied to electronics industry.It is about 10 that the number-average molecular weight of thermoplastic polymer should be, 000-100,000.If number-average molecular weight is far below about 10,000, binder composition just unlikely forms the bonding film of easy handling so.If number-average molecular weight is much larger than about 100,000, the viscosity of binder composition can rise and makes and be difficult to tackiness agent is painted membranaceous that and thermoplastic polymer can descend in the solubleness of aromatic polyepoxide so.Preferably, thermoplastic polymer is an aromatics, thereby can provide thermostability better tackiness agent bonding film.When being exposed to electron beam irradiation, thermoplastic polymer also should not react.
The thermoplastic polymer that is applicable to binder composition of the present invention and tackiness agent bonding film comprises polysulfones, for example by with 4,4 '-dichloro diphenylsulfone and 2, two (4-hydroxy phenyl) the propane copolymerizations of 2-and the polysulfones that forms; Poly-(methyl methacrylate); The phenoxy group polymkeric substance, as with 2, two (4-hydroxy phenyl) propane of 2-and its diglycidyl ether copolymerization and the polymkeric substance that obtains; The mixture of polycarbonate and these materials.
The example that can be used for commercially available thermoplastic polymer of the present invention has: PKHP
TM200 (PhenoxyAssociates, Rock Hill, SC), PKHJ
TM(Phenoxy Associates), UDEL
TM1700 and UDEL
TM3500 (all from Amoco Performance Products, Inc., Ridgefield, CT), PLEXIGLASS
TM(Rohm﹠amp; Haas, Philadelphia, PA) and LEXAN141 (General ElectricCo.).
Binder composition of the present invention and tackiness agent bonding film also contain polyfunctional (methyl) acrylate." (methyl) acrylate " refers to have the compound of acrylate or methacrylic acid ester moiety, the compound that promptly has following groups:
Wherein R is hydrogen or methyl, and R ' is an organic radical." multifunctional " refer to compound have at least two (methyl) acrylate-based.
Be used for multifunctional (methyl) of the present invention acrylate and be preferably dual functional, thereby can form two (methyl) acrylate.When using different multifunctional (methyl) acrylate mixtures, can for example be used to regulate the viscosity of binder composition with (methyl) acrylate of a spot of simple function so that apply.Yet too much simple function (methyl) acrylate can cause the mobile and/or binding property decline of over-drastic in the curing process.
Aromatics can use with (methyl) aliphatic series acrylate.Preferably (methyl) acrylate is an aromatics, thereby dissolves in the aromatic polyepoxide before being exposed to electron beam irradiation, and the Heat stability is good of the tackiness agent bonding film of thermofixation.Preferably multifunctional (methyl) acrylate dissolved in the aromatic polyepoxide before electron beam irradiation.Further preferably, it is liquid that multifunctional (methyl) acrylate at room temperature is essentially, and is convenient to mix and apply this binder composition like this.If binder composition can be in room temperature or mixed under the condition of heat a little and apply, can use solid-state multifunctional (methyl) acrylate so.
Being used for suitable multifunctional (methyl) acrylate of the present invention comprises: dihydroxyphenyl propane two (methyl) acrylate of bisphenol-A epoxy two (methyl) acrylate, ethoxylation, tetramethylolmethane four (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triglycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, epoxy phenolic varnish many (methyl) acrylate etc.Preferably multifunctional (methyl) acrylate comprises two (methyl) acrylic ester compound of dihydroxyphenyl propane base, as dihydroxyphenyl propane two (methyl) acrylate of bisphenol-A epoxy two (methyl) acrylate and ethoxylation.
Be applicable to that commercially available multifunctional (methyl) acrylate example of the present invention has: from Sartomer Co., Exton, the SARTOMER of PA
TMSeries material such as SARTOMER
205, SARTOMER
231, SARTOMER
238, SARTOMER
239, SARTOMER
348 and SARTOMER
349, and from UCB Redcure, Inc., Smyrna, the EBECRYL of GA
TMFamily's material such as EBECRYL600, EBECRYL616 and EBECRYL639.
Binder composition of the present invention and tackiness agent bonding film also can randomly contain the double reactive compound, although this compound is quite favourable.This compound contain exactly at least one (methyl) acrylate-based and at least one can with the compound of the group of aromatic polyepoxide reaction.The double reactive compound can improve the binding property of final tackiness agent bonding film.The double reactive compound should dissolve in the aromatic polyepoxide before electron beam irradiation.Double reactive compound aromatics and aliphatic series all can use.Yet the double reactive compound is preferably aromatics, thereby can improve the solubleness in aromatic polyepoxide before being exposed to electron beam irradiation, and can improve the thermostability of final tackiness agent bonding film.Further preferably, it is liquid that the double reactive compound at room temperature is essentially, and is convenient to like this mix and the application of adhesive composition.If binder composition can be in room temperature or mixed under the condition of heat a little and apply, can use solid-state multifunctional double reactive compound so.
Be used for the double reactive compound, can comprise with the example of the group of polyepoxide reaction: hydroxyl, carboxyl, amido (especially ah aromatic amihe-based) and 1,2-epoxy group(ing).The object lesson that can be used for double reactive compound of the present invention has: the acrylic ester compound with carboxylic-acid functional as (methyl) vinylformic acid and (methyl) acrylate of containing phenyl with hydroxyl-functional as (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester and 2-hydroxyl-3-phenyl phenoxy group (methyl) acrylate.Also spendable is two (methyl) acrylate that the front is described as suitable multifunctional (methyl) acrylate, can be replaced with the group of polyepoxide reaction when one of them (methyl) is acrylate-based.This examples of substances comprises: glycidyl (methyl) acrylate, epoxy phenolic varnish (methyl) acrylate, triglycol (methyl) acrylate etc.Especially preferably as the double reactive compound be one (methyl) acrylate of various poly epoxy resins, as bisphenol-A epoxy one (methyl) acrylate etc.The example that is applicable to commercially available double reactive compound of the present invention has EBECRYL
TM3605 (UCB Radcure Inc.) and SARTOMER
TM370 (Sartomer Co.)
Use the hot activation solidifying agent that solidifies significant quantity, thereby in final tackiness agent bonding film, provide required high-temperature behavior, and required high-temperature behavior depends on the purposes of tackiness agent bonding film.The actual amount of solidifying agent also is subjected to the influence of the type and the quantity of other components in the mixture.The tackiness agent bonding film of the formed thermofixation of small number of curing agents, its second-order transition temperature is low, the thermal expansivity height, and also good solubility-resistence descends.A large amount of solidifying agent except cause solidifying very fast and may uncontrollable heating, the final tackiness agent bonding film that forms can absorb too many moisture, quality is crisp and second-order transition temperature is low.
In these parameter areas, per relatively 100 parts by weight aromatic polyepoxides, the common consumption of solidifying agent is about 2-110 parts by weight.When solidifying agent was the Lewis acid type, its typical amounts was that per relatively 100 parts by weight aromatic polyepoxides are the 0.1-5 parts by weight.When solidifying agent is carboxylic acid, acid anhydrides or primary amine or secondary amine, then be equivalent to whenever the amount epoxy group(ing), solidifying agent is generally about 0.5-1.7 angelic acid, acid anhydrides or amine.For anhydride type curing agent, can there be the optional accelerator of about 0.1-5 parts by weight in per relatively 100 parts by weight aromatic polyepoxides; As aromatic uncle amine such as benzyl dimethyl amine or imidazoles such as 2-ethyl-4-methylimidazole.
The consumption of thermoplastic polymer is a significant quantity, this represent this quantity be enough to provide can mixed coated then (as applying) binder composition, and can not cause the premature reaction of polyepoxide solidifying agent, thereby form the bonding film of easy handling.This bonding film subsequently can be by thermofixation under the situation of control adhesive flow.
Quite advantageously, binder composition of the present invention only needs a spot of thermoplastic polymer.Although depend on the type of other components in the binder composition and the end-use of quantity and tackiness agent, actual amount can change, but the typical amounts of thermoplastic polymer is preferably about 20-40 parts by weight, preferably be about 20-30 parts by weight, by per 100 parts by weight aromatic polyepoxides.When being higher than about 40 parts by weight thermoplastic polymers, the mixing of binder composition and application temperature can rise to the temperature of too early generation thermofixation, and the tackiness agent bonding film that forms can be too crisp and be difficult to operation.When being less than the thermoplastic polymer of about 20 parts by weight, the tackiness agent bonding film can be difficult to operation, and adhesive flow is excessive in curing process.
The consumption of multifunctional (methyl) acrylate is a significant quantity, and this represents that this quantity is enough to the binder composition that provides such, and it can form the bonding film of easy handling, and this bonding film subsequently can be by thermofixation under the situation of control adhesive flow.In these parameters, the consumption of multifunctional (methyl) acrylate is preferably about 5-20 parts by weight, preferably is about 12-20 parts by weight, by per 100 parts by weight aromatic polyepoxides.Although actual amount depends on the end-use of the type of other components in the binder composition and quantity and tackiness agent and changes.When being less than multifunctional (methyl) acrylate of about 5 parts by weight, the tackiness agent bonding film of formation can be difficult to operation, and adhesive flow is excessive in curing process.When consumption was higher than about 20 parts by weight, the tackiness agent bonding film can be difficult to operation, and the thermofixation meeting produces the low and high temperature (as the high temperature that runs into) of the binding property composition of poor stability down in the electric welding process of printed circuit board (PCB).
The consumption of double reactive compound (when existing) is a significant quantity, and this represents that this quantity is enough to the binder composition that provides such, and it can form the bonding film of easy handling, and this bonding film subsequently can be by thermofixation under the situation of control adhesive flow.In these parameters, the consumption of double reactive compound is preferably about 1-15 parts by weight, preferably is about 4-10 parts by weight.Although depend on the type of other components in the binder composition and the end-use of quantity and tackiness agent, actual amount can change.When being less than about 1 parts by weight, the tackiness agent bonding film of thermofixation can lose viscosity.During greater than about 15 parts by weight, the tackiness agent bonding film can be difficult to operation, and adhesive flow is excessive in curing process.
The significant quantity of multifunctional (methyl) acrylate and double reactive compound (when existing), also by the quantity decision that is used in combination, effective mixing consumption of these two kinds of materials is enough to provide the tackiness agent bonding film, this bonding film easy handling and can be changed into the heat-staple material with good bond strength by thermosetting.General multifunctional (methyl) acrylate and the double reactive compound that uses about 10-25 parts by weight is preferably for about 15-20 parts by weight, by per 100 parts by weight aromatic polyepoxides.Although depend on the type of other components in the binder composition and the end-use of quantity and tackiness agent, actual amount can change.When the mixing consumption of multifunctional (methyl) acrylate and double reactive compound was less than about 10 parts by weight, the tackiness agent bonding film of the thermofixation of formation was difficult to operation.When the mixing consumption of multifunctional (methyl) acrylate and double reactive compound surpassed about 25 parts by weight, then the tackiness agent bonding film was easy to be torn, and the thermostability of the tackiness agent bonding film after the thermofixation is low and binding property is low.
Multifunctional (methyl) acrylate is between about 95: 5 to 50: 50 to the weight ratio of double reactive compound (when existing).Preferably about 80: 20-50: between 50, be about 80 best: 20-75: 25.When weight ratio surpassed 95: 5, the tackiness agent bonding film of formation can be difficult to operation, and the binding property of the tackiness agent bonding film after the thermofixation is low.When weight ratio during less than 50: 50, the tackiness agent bonding film can be difficult to operation, and adhesive flow is excessive in curing process.
Can in binder composition of the present invention and tackiness agent bonding film, mix various additive, so that give different useful property.Suitable additive comprises: fire retardant, conductive particle, heat conduction particle, pigment, hollow or solid microsphere polymkeric substance or inorganic, mineral filler, antioxidant and braided fabric or nonwoven fabric as making with carbon, glass or polyaramide material.
Binder composition of the present invention and tackiness agent bonding film can conveniently be produced.Large-scale mixing tank (mogul) with forcing machine, planetary-type mixer or heating mixes various compositions, forms to have the mixture that can apply viscosity.Each composition can add successively.Preferably, aromatic polyepoxide and thermoplastic polymer mix in solution, add multifunctional (methyl) acrylate and double reactive compound (if containing) then, add solidifying agent at last.Do not need solvent.Therefore binder composition of the present invention can 100% solid mixture form provide.
Preferable and quite advantageously, can select aromatic polyepoxide, thermoplastic polymer, multifunctional (methyl) acrylate and double reactive compound (if existence) to make it solvable mutually.Hot activation solidifying agent solubilized or be scattered in these components.Solvable, this is illustrated in and mixes soluble material (can heat if desired) and make the temperature of mixture return after the room temperature evidence that detects by an unaided eye and at room temperature do not have visible to be separated.Lacking solvability can be evidence with bond strength heterogeneity, membrane operations poor performance, poor adhesion and the controlled difference of adhesive flow.The each component (except the polyepoxide solidifying agent, if its dispersed word) that constitutes binder composition is mixing and is painting after membranaceous soluble still the time.
Because binder composition of the present invention does not rely on actinic radiation to form the tackiness agent bonding film, so said composition does not need photocatalyst.Thereby binder composition of the present invention and tackiness agent bonding film are that light is stable.In other words, they are very inactive when being exposed to visible light or ultraviolet ray, therefore no longer need pack and store (as being stored in the light tight or ultraviolet container) under the condition of " safe light ".
In case mixed various compositions, can become membranaceous the transfer goods are provided by binder composition being applied (as applying) so, as be coated on the removable release liner or be coated between two release liner (having identical or different demoulding values).Useful release liner comprises siliconised paper and plastic film.Perhaps, binder composition is coated on the permanent backing, backing can the time make with materials such as polyolefine, polyester, polyimide or paper for example.If desired, can carry out prime treatment as with chemical priming paint or corona discharge to backing.The adhesive surface that exposes can be protected with removable release liner (for example recited above).In another example, by the layer of adhesive composition being coated in (as carbon, glass, fragrant acid amides (aramide), polyester or polyimide fiber) on stitch bonded fabric or the nonwoven fabric area supported, such as flood this supporting material with binder composition, can make fibre-reinforced composite product.
Binder composition of the present invention can be painted membranaceous with various technology, as with applying method (being coated with method (die coating) as hot scraper-bed formula method (knife-over-bed), roller coat and mould).Advantageously, this binder composition can preferably for about 30-120 ℃, be more preferably about 30-90 ℃ under lower temperature (promptly about room temperature is to about 120 ℃), under about 30-60 ℃, apply best, thereby can prevent that hot activation polyepoxide solidifying agent from reacting too early.Coat-thickness is about 10-130 micron or thicker.
In case binder composition is coated with membranaceous, so just can electron beam irradiation for some time, exposure level should be enough to make (methyl) acrylate in multifunctional (methyl) acrylate and the double reactive compound (if existence) that polymerization and crosslinked partly takes place, but can not cause hot activation solidifying agent, aromatic polyepoxide or (more preferably) thermoplastic polymer to react.Typical radiation parameter is about 2-10 megarad (Mrad).Can use 5Mrad.It is that glue or not sticking that the tackiness agent bonding film feels, and this depends on concrete types of compositions.
Be exposed to electron beam irradiation and can in unreacted aromatic polyepoxide, form (methyl) acrylic ester polymer net, because (methyl) acrylate-functional component is dissolved in the aromatic polyepoxide before irradiation the time.(methyl) acrylic ester polymer net and thermoplastic polymer contribute to the tackiness agent bonding film of the preferred easy handling of the present invention.These tackiness agent bonding films can take off from interim carrier (as release liner), place then on the substrate and fold can not take place, tear or nonvolatil stretching (promptly not having the change of nonvolatil size or thickness aspect).Can the tackiness agent bonding film be taken off from interim carrier by the method for craft or automation, although last method needs film that excellent operating performance is arranged, because the power that puts in the process of taking off on the film is uneven.After being exposed to electron beam irradiation, have the modulus of about 1-300 megapascal (MPa) (MPa) and second-order transition temperature and be about 20 ℃ or lower, can help forming tackiness agent bonding film with acceptable operating performance.
Tackiness agent bonding film of the present invention can be used for bonding dissimilar material, comprising: stitch bonded fabric and nonwoven fabric (as glass, carbon and fragrant acid amides), metal (as aluminium, stainless steel and copper), plastics (as polyimide and polyester) and pottery.Binder composition of the present invention and tackiness agent bonding film can be used for forming by fibrous reticulum or fibrous bundle enhanced composite product, and are generally used for industrial bonding application as making (high-intensity) structural sheet pressing plate.The tackiness agent bonding film is particularly useful for electron trade.A kind of particularly preferred purposes is to make laminated printed circuit board (PCB), and wherein the tackiness agent bonding film is used to copper-plated polymkeric substance (as the polyimide) plaque layer that contains etched circuit is forced together.Other particularly preferred purposes comprise: integrated circuit (IC) chip and flexible circuit are sticked on the inflexible printed circuit board (PCB), and printed circuit board (PCB) is bonded together mutually.
When tackiness agent is prepared between two release liner when forming transferable tackiness agent bonding film, a release liner is taken off, the tackiness agent bonding film placed treat on the adherent substrate, take off second release liner, again second substrate placed on the tackiness agent.When tackiness agent comprises the release liner of permanent backing (it provides a substrate) and protectiveness, lining can be taken off, relative second substrate of binder layer placed.
In case the tackiness agent bonding film is with respect to treating that the adherent substrate is by suitable placing, so just can heat for some time (being enough to solidify aromatic polyepoxide) at a certain temperature, actual time and temperature depend on the concrete component in the binder composition and treat the adherent substrate.Generally can use about 50-250 ℃ temperature, be about 20 seconds-5 hours set time, and higher temperature needs still less set time than lesser temps usually.Can use 180 ℃ of conditions of cure that solidify 90 minutes.
Polymerization already and crosslinked (methyl) acrylic ester polymer net and thermoplastic polymer are given preferred adhesive bonding film of the present invention with adhesive flow in the curing process controlled, and this causes forming uniform bonding coat and bond strength.The tackiness agent bonding film of thermofixation can have high-temperature behavior, and these performances do not have notable difference with the high-temperature behavior that does not contain the heat-curable epoxy resin of (methyl) acrylate component.Therefore, the tackiness agent bonding film of thermofixation of the present invention can be exposed to high temperature, as the high temperature that runs in the printed circuit board (PCB) welding process.
In conjunction with the following embodiment that does not provide constraints, can understand the present invention more fully.Describe now and be used to prepare and test binder composition, tackiness agent bonding film and with the current techique of its veneer sheet that makes.Be of a size of specified size, it is more rough that English unit is converted into international unit.
The general preparation of binder composition, tackiness agent bonding film and veneer sheet
The general preparation process of binder composition
With aromatic polyepoxide 950 watts microwave oven (R E53C002 type, the Hotpoint board, HotpointCompany, Louisville, KY) in, in the highest heating 60 seconds that are provided with down, make viscosity be convenient to topple over, so that weighing and transfer.Resin temperature can not be above 70 ℃.With 0.2 liter of metal tin, pneumatic blending machine and hot-plate, thermoplastic polymer is dissolved in the aromatic polyepoxide of 120 ℃ of resin temperatures.Dissolving the required time is generally 20-30 minute.Detecting the dissolved standard is to form limpid, uniform solution.
With low speed mixing process or high-speed mixing process, multifunctional (methyl) acrylate is mixed with aromatic polyepoxide/thermoplastic polymer mixtures mutually with double reactive compound (when comprising).
In the low speed mixing process, multifunctional (methyl) acrylate and each leisure of double reactive compound are set in heating in advance in 70 ℃ the convection of air stove, until reaching dumpable viscosity.These compositions of weighing place 8 ounces of glass cylinderes then, mix with wooden spatula by hand.The also heating in advance in being set in 70 ℃ convection of air stove of aromatic polyepoxide and thermoplastic polymer mixtures, until reaching dumpable viscosity, when reaching this viscosity it is added to capacity and be 60 grams, cam mixing oar be housed and be preheated to 60 ℃ Plasti-corder
TMThe PL-2000 mixing tank (C.W.Brabender Instruments, Inc., Hackensack, NJ).In this process with when all add material later on, mixing velocity all is 30 rev/mins (rpm).After 1-2 minute, add multifunctional (methyl) acrylate/double reactive compound of preheating, mixed 1-2 minute at 60 ℃ again.Then, slowly add the polyepoxide solidifying agent, between each the adding, stir with every part one soupspoon.Every part of solidifying agent is disperseed fully, so that eliminate all visible " caking (clump) " before the portion under adding.After adding all solidifying agent, mixing velocity is risen to 100rpm, mixed 5 minutes.
The high-speed mixing process can prepare sample quickly.More specifically, with wooden spatula at room temperature multifunctional (methyl) acrylate of manual mixing and double reactive compound.Aromatic polyepoxide/thermoplastic polymer mixtures is at 720 watts of microwave oven (ERS-6831B types, the Toshiba board, Toshiba America, Wayne, NJ) in, heated 15 seconds down, take out, stir a little with wooden spatula by hand in the highest setting, and then heated 15 seconds, reach dumpable viscosity so that weighing and transfer.Mixing temperature is no more than 70 ℃.Dumpable aromatic polyepoxide/thermoplastic polymer is taken by weighing the plastics of putting into 0.05 liter mix cup, add multifunctional (methyl) acrylate/double reactive compound then.These compositions be equipped with the metal spatula and with the Cordless Drive Drill of 1100rpm running (Model 6211DW, Makita Corporation, Japan) in, thorough mixing is about 30 seconds under room temperature.Then, in the polyepoxide solidifying agent adding plastic cup with all amts, be no more than about 2 minutes with wireless brill (cordless drill) high-speed mixing, solidifying agent is fully disperseed until there not being the visible block.Described in the high-speed mixing method, 5-10 is once warm once in a while second at interval to mixing material in the cup with microwave oven.
The general preparation process of tackiness agent bonding film
The preparation of tackiness agent bonding film can be passed through the application of adhesive composition, then the tackiness agent that applies is exposed to electron beam irradiation.
More specifically, with scraper-bed formula (knife-over-bed), 6 inches wide, heating coating workstation (coatingstation) application of adhesive composition.Scraper is locked in the normal position to keep the fixed gap.Bed and scraper all contain heating unit, and radiation heater is equipped with at the position of placement tackiness agent behind scraper.Two heating units (Watlow Firerod cartridge heater, G5A115 type, 125 watts are arranged in bed; Watlow, St.Louis MO), and has 3 heating units (Watlow band heater, STB1E1E2 type) to be wound on 3/4 of scraper periphery.A thermopair is installed below bed one side scraper, and another thermopair contacts with the surface of radiation heater.The well heater of bed and scraper is all controlled by Watlow Series 965 temperature controllers that are set in 65 ℃, and radiation heater is controlled by the controller that another is set at 140 ℃.With clearance gauge (feelergauge claims thickness piece again) scraper gap is set at combined thickness big 0.002 inch (50 microns) than 2 used release liner.
Described in top high-speed mixing method, warm binder composition is 15 seconds in microwave oven, and it can be toppled over.Then binder composition is poured on that two 0.002 inch (50 microns) are thick, between the polyester release liner that scribbles silicone.Radiation heater is placed after this " sandwich " superstructure, allow temperature equilibrium 0.5-1 minute, until the viscosity of binder composition that detects by an unaided eye to obtain to apply.Then, the release liner that has binder composition in the centre is pulled between scraper and bed, under scraper extrusion bonded dose.
With running speed be 25 feet (7.6 meters)/minute Electro Curtain Model CB300/30/380 (the titanium window: 2.5 inches (6.4 centimetres) are long, 14 inches (36 centimetres) are wide, Energy Sciences, Inc., Wilmington, MA) equipment sees through release liner, tackiness agent after applying is exposed to electron beam irradiation since a side, to form tackiness agent bonding film of the present invention.Electron beam processing is under nitrogen purge gas and room temperature, finishes with rumbatron (working dosage=5 megarads under 250 dried volts and 5 milliampere(mA)s).Whole exposure duration is about 0.5 second.
The general preparation process of veneer sheet.
The tackiness agent bonding film is used to make copper-plated polyimide membrane laminate.All copper, polyimide film, release liner and metal sheet surface are all used tack cloth or Kimwipes
TM(Kimberly-Clark Corporatioin, Atlanta GA) carry out wiping to-EX-L Delicate Task Wiper, so that remove dust before use.
More specifically, cut that a pair of about 0.002 inch (50 microns) are thick, the tackiness agent bonding film of 5 inches * 5 inches (13 centimetres of 13 cm x), expose a surface of every bonding film by taking off a slice release liner then.The tackiness agent bonding film is placed the Kapton of a slice 6 inches * 6 inches * 0.001 inch thick (15 cm x, 15 cm x, 25 micron thickness)
TMFPC-ZT polyimide film (E.I.DuPont deNimours and Company, Wilmington, both sides DE).Take off second release liner from each tackiness agent bonding film, it is that 6.5 inches * 6.5 inches (16.5 centimetres of 16.5 cm x) 1 ounce copper foil are (from Oak-Mitsui that the polyimide film that will be coated with tackiness agent then places 2 layers of size, Class 3 types are through the TOB polishing) between.Copper foil layer is directed placement, thereby makes crystalline orientation (grain direction) all identical in both sides.
The sandwich (layup) of Copper Foil/tackiness agent bonding film/polyimide film/tackiness agent bonding film/Copper Foil is placed the release liner (Tedlar of 27 inches * 7 inches (17 centimetres of 17 cm x)
TMMR is from E.I.DuPontdeNimours and Company) between.Assembling contains the group cover of 2-6 such sandwich (placing a metal division board between each sandwich), metal base plate and metal decking.Base plate is of a size of 8 inches * 8 inches (20 centimetres of 20 cm x); The size of panel and division board all is 6 inches * 6 inches (15 centimetres of 15 cm x).The thickness of all plates all is between 0.040 to 0.062 inch (1.02-2.57 millimeter).Come the hot setting adhesive bonding film with a kind of in two kinds of different methods then.Under two kinds of methods, all use 8 inches * 8 inches (20 centimetres of 20 cm x) single radial cuts laminating machine (Pasadena Hydraulics, Inc., (PHI), industrial city, CA, TS-21-H-C-8 type; Has DT5000 temperature controller/sequencer).After thermofixation, veneer sheet is cut into 4.5 inches * 4.5 inches (11.4 centimetres of 11.4 cm x).
In a kind of laminating method (being called laminating method A herein), group is enclosed within the room temperature and is placed in laminating machine.Apply 50 pounds/square inch pressure at once, and the speed that begins with 5 ℃/minute is heated to 180 ℃.Group is enclosed within 180 ℃ and kept 90 minutes, with tap water heated platen is cooled to room temperature internally then in 5 minutes.
Second kind of laminating method (being called laminating method B herein) is identical in laminating method A, and difference is: laminating machine is programmed to be heated to 190 ℃ and group and is enclosed within and kept under this temperature 30 minutes.After being cooled to room temperature, veneer sheet is transferred in the convection of air stove of preheating, 180 ℃ of after fixing 90 minutes.
Testing method
Second-order transition temperature (Tg)
(New Castle DE) measures the Tg of the tackiness agent bonding film of thermofixation for 2920 types, TA Instruments with the differential scanning calorimeter (DSC) of single cell.About 5-15 milligram tackiness agent bonding film is placed the DSC sample disc, and sealing was also heated 90 minutes in 180 ℃ in the convection current air furnace of preheating.Then under the helium purge gas from 40 ℃ to 250 ℃, with 20 ℃/minute speed sample is scanned.Tg is half height that changes in the scanning for the first time.The numerical value degree of being scaled of report.
Peel adhesion strength
The peel adhesion strength of the veneer sheet testing method-650 of The Institute for Interconnecting and PackagingElectronic Circuits (PIC), No.2.4.9, revision D (10/88): " PeelStrength; Flexible Printed Wiring Materials; Method A (With Sliding Plate TestFixture) " measures, and except following change is arranged: veneer sheet is of a size of 2.25 inches * 2.75 inches (6.99 centimetres of 5.72 cm x); Test 3 and peel off band; Peel off band collection data (120 data points) on 2.0 inches (5.1 centimetres) distances for each; Before analyzing, give up each and peel off band preceding and the most last 0.17 inch (0.43 centimetre) (each 20 data point) with Mitutoyo Digimatic Mini-Processor (DP-2DX type).Each average stripping strength of peeling off band is used to calculate 3 population means of peeling off band, and the mean value of report is to be similar to 0.1 pound of/inch width (piw).
The preparation of release adhesive specimen be by: carve in a lateral erosion of veneer sheet and to peel off band.Side at veneer sheet is coated with 3 inches 3M Scotch that (7.6 centimetres) are wide fully
TM1280 Circuit Plating Tape (circuit card adhesive tape).The wet Heavy Duty 3M Scotch-Brite of opposite side at veneer sheet
TMScourPad (catalogue #220) cleans and roughening, dries with paper handkerchief then.Use a slice 3M Scotch again
TMLength one lateral edges of 1280 CircuitPlating Tape sealer coat pressing plates forms a border (a slice adhesive tape is respectively used in both sides) along the laminate surface length direction of roughening.Then, with 0.125 inch 3M Scotch that (0.318 centimetre) is wide
TM218 Fine Line Tape (thin adhesive tape) shelter 8 parallel testing bands along the length direction of sample uneven surface, and they are 0.125 inch (0.138 centimetre) at interval.With the spatula thin adhesive tape that gently rubs, thereby remove all spaces and make the wetting copper of binder tape surface fully.With the naked eye look to be exactly the surperficial deepening under the adhesive tape.
The veneer sheet that has adhesive tape, with containing iron trichloride etching reagent (catalogue #E-4G, KEPRO CircuitSystems, Inc.) KEPRO Bench-Top etching instrument (BTE-202 type, KEPRO Circuit Systems, Inc., Fenton, MO), etching is 3 minutes under the condition of 43 ℃ and pH1, to remove unshielded copper.If copper is still stayed the not masking regional of veneer sheet, so with veneer sheet Rotate 180 degree on specimen holder, and then etching 1 minute is to remove residual unshielded copper fully.Take out etched sample then, earlier with water-bath rinsing from the beginning 1 minute, rinsing 1 minute in the mobile tap water then, then dry air.Take off all adhesive tapes from sample, do not cause the crooked or damage of sample.
Etched veneer sheet Copper Clad Peel Tester (tester is peeled off in copper facing) (the TA-630 type that 2 pounds of ergometers are housed; CECO Industries, Anaheim CA) tests.Sample is installed on the sliding bearing platform the facing up of copper calibration tape.Arranged veneer sheet, fixed with slotted cover plate, cover plate is securely fixed on the supporting station.Copper calibration tape on the veneer sheet is located under 0.188 inch (0.476 centimetre) wide notch, and passes notch and link to each other with ergometer.Slip clamp and ergometer are an angle of 90 degrees mutually.Sample with 2 inches (5 centimetres)/minute speed peel off.For being used for electron trade, the release adhesive degree is at least 6.0piw, more preferably is at least 8.0piw.For other purposes, the release adhesive degree is less also to be acceptable.
Membrane operations
0.5 inch * 5.0 inches (12.7 centimetres of 1.3 cm x) samples are taken off from release liner, and bimanual thumb and forefinger are arrested, and both hands are 1 inch (2.5 centimetres) at interval, carry out tractive then until breaking.Determine stretch-proof and resistance to tearing qualitatively, and provide relative grade.
Grade is that the 3+tackiness agent bonding film of (+++) shows medium stretch-proof and resistance to tearing.Take off lining or take off and to finish easily, and fold can not take place, tear or nonvolatil stretching (promptly not having the change of nonvolatil size or thickness aspect) in film from lining.The tackiness agent bonding film can be operated easily with automatic machinery or manual method.
Grade is the 2+tackiness agent bonding film of (++), compares with (+++) sample, shows lower stretch-proof and resistance to tearing.Take off lining or take off (and the tackiness agent bonding film fold can not take place, tears or nonvolatil stretching) the most handy automatic machinery or careful manual operations is finished from lining.
Grade is that the 1+tackiness agent bonding film of (+) is considered to only be suitable for the automatic machinery method of operating, take off and the tackiness agent bonding film fold can not take place, tears or nonvolatil stretching from lining guaranteeing, because with grade be 3+with 2+sample compare, its stretch-proof is lower.
Grade be 1,2 or 3+the tackiness agent bonding film can be used as transfer film (promptly being carried at the tackiness agent bonding film between a pair of release liner or other the interim carriers), or use with permanent backing.Grade be 2 or 3+the tackiness agent bonding film also can be used as independent film, promptly can physically take off from the carrier (as release liner or other interim carriers) and operate under the situation of carrier not having.Taking off lining or fold takes place when lining takes off, tearing, crease or water property of a specified duration tensile tackiness agent bonding film is cited as negative (-), think to be difficult to be taken off, but can be used for contact laminating needn't take off film earlier in permanent backing (especially those porous) from release liner occasion with automatic machinery or manual method.
The performance characteristic of some tackiness agent bonding film is also assessed by the modulus of measuring them.More specifically, (TA Instruments Inc.) obtains Young's modulus under the room temperature with the hot machine analysers of 2940 types (TMA).Sample size is: length=0.16-0.50 inch (4.0-12.7 millimeter), about 0.002 inch of thickness (50 microns).Width: length ratio is 1: 6 or bigger (as 1: 8), so that meet test request.Sample is placed under 0.001 newton's the power that applies (stress), measures initial length.Then with 1.0 newton/minute speed power is increased to 1.0 newton, note the variation (strain) of length.Select the length of sample, sample is ruptured under 1 newton or the littler power that applies.According to stress the initial slope meter of strain curve is calculated modulus, approximate to 0.1MPa.Preferably, the modulus of tackiness agent bonding film of the present invention is that about 1-300MPa is so that there is good processing property.
Adhesive flow
In curing process, binder composition takes place to flow.Adhesive flow to a certain degree needs, so that the even bonding coat that wetting substrate surface and formation have the homogeneous bond strength.But meeting over-drastic adhesive flow can make tackiness agent ooze out the edge of substrate or form uneven bonding coat, space or uneven bond strength in curing process, and this should be avoided when making veneer sheet.Yet the degree of the adhesive flow that can tolerate depends on the end-use of binder composition.For example, if binder composition of the present invention or tackiness agent bonding film are used to impregnation of fibers enhanced net or bundle, can allow adhesive flow greatly so.
The degree of adhesive flow before cutting after laminating machine takes off and for release adhesive test at veneer sheet, detects by an unaided eye veneer sheet and is determined.The grade that describes below is relative.
More specifically, tackiness agent bonding film (before thermofixation) and the distance between the Copper Foil outward flange at initial centering is 0.75 inch (1.91 centimetres).If after thermofixation, be 0.5 inch (1.27 centimetres) from Copper Foil outside genesis adhesive flow, so just give 2+grade (++), this expression adhesive flow degree is low.If from Copper Foil outside genesis tackiness agent be 0.5 inch (1.27 centimetres) to 0.125 inch (0.32 centimetre), so just give 1+grade (+), this expression adhesive flow degree is medium.1+and 2+grade all be illustrated in best adhesive flow control performance arranged when being used for the vital bonding occasion of this performance.When tackiness agent apart from the outer peripheral distance of Copper Foil less than 0.125 inch (0.32 centimetre) or when having oozed out the Copper Foil edge, provide negative (-) grade, this shows the adhesive flow height.
Word
In the following example, use various abbreviations.These abbreviations with under list and define:
CAF-9,9 '-two (3-chlorine 4-aminophenyl) fluorenes
CG-140-Dyhard RU 100 (from Air Products)
D.E.H.
TM85-phenol cured agent (from Dow Chemical Company)
D.E.N.
TM438 (from Dow Chemical Company)
D.E.R.
TMThe diglycidyl ether of 332-dihydroxyphenyl propane (from Dow Chemical Company)
EBECRYL
TMOne acrylate of 3605-dihydroxyphenyl propane diglycidyl ether (from UCB RadcureInc.)
EPON
TMThe diglycidyl ether of 828-dihydroxyphenyl propane (from Shell Chemical Company)
The GMA-glycidyl methacrylate (can be used as SARTOMER
TM379, obtain from SartomerCompany)
HDDA-diacrylate 1,6-hexylene glycol ester (can be used as SARTOMER
TM238, obtain from SartomerCompany)
The IBA-isobornyl acrylate (can be from San Esters Corporation, New York, NY obtains)
The IBMA-isobornyl methacrylate (can be used as SARTOMER
TM423A obtains from SartomerCompany)
P3500-Udel
TMP3500 gathers (ether-sulfone) (can be from Amoco Performance Prroducts, Inc. obtains)
PEA-vinylformic acid 2-phenoxy ethyl (can be from CPS Chemical Company, Old Bridge, NJ obtains)
PhEMA-methacrylic acid 2-phenoxy ethyl (can be used as SARTOMER
TM340, obtain from SartomerCompany)
PKHJ
TM-phenoxy resin (can obtain) from Phenoxy Associates
PMMA-gathers (methyl methacrylate) (molecular weight=33,000; Can be from Scientific Polymer Products, Inc., Ontario, NY obtains)
PolyEMA-gather (Jia Jibingxisuanyizhi) (can obtain from Aldrich Chemical Company, catalogue #18,208-7)
QUATREX
TMThe diglycidyl ether of 1010-dihydroxyphenyl propane (from Shell Chemical Company)
The TEGDMA-triethylene glycol dimethacrylate (can be used as SARTOMER
TM205, obtain from SartomerCompany)
THFA-vinylformic acid tetrahydrofuran ester (can obtain) from San Esters Corporation
ULTEM
TM-100-gathers (ether-imide) (can obtain from General Electric Company, be converted into big or small about 5 microns or littler fine particle by the emulsification precipitator method (as in U.S. Patent No. 5,276, the method described in 106) then)
XU AY238-epoxy glycolylurea (can be from Ciba Geigy, Inc. is with trade(brand)name ARACAST
TMObtain)
Unless indicate in addition, all quantity all is that the umber that calculates by 100 parts by weight aromatic polyepoxides is parts by weight in the following example, and is approximated to immediate integer.
Embodiment 1-17
By the described such a series of veneer sheet for preparing of top " the general preparation of binder composition, tackiness agent bonding film and veneer sheet " part, be listed in the following table 1.Based on the description that provides above, table 1 has shown laminating method and blending means, and the latter is divided into " HS " (at a high speed) or " LS " (low speed).In each embodiment, binder composition contains D.E.R.
TM332 aromatic polyepoxides, CAF hot activation aromatic polyepoxide solidifying agent, PKHJ
TMThermoplastic polymer, multifunctional (methyl) acrylate (dimethacrylate of the dihydroxyphenyl propane diglycidyl ether of 90: 10 (w/w) and the mixture of TEGDMA) and EBECRYL
TM3605 double reactive compounds.The relative populations of every kind of component is listed in the table below in 1.The merging quantity of multifunctional (methyl) acrylate and double reactive compound can change, although the weight ratio of these two kinds of components was kept 80: 20 always.Embodiment 1-8 contains 30 parts by weight thermoplastic polymers, and embodiment 9-12 contains 25 parts by weight, and embodiment 13-17 contains 20 parts by weight.
Assess one or more following performances of each embodiment with above-mentioned testing method, and the result is beneficial in the following table 1: membrane operations, modulus (megapascal (MPa) or MPa), adhesive flow control, second-order transition temperature (Tg, ℃) and peel adhesion (pound/inch width, piw).Embodiment 1 does not have coated one-tenth membranaceous, and is not exposed to electron beam irradiation to form the tackiness agent bonding film.
Table 1
| Embodiment | Binder composition | Specimen preparation | Test result | |||||||||
| Aromatic polyepoxide | Solidifying agent | Thermoplastic polymer | Multifunctional (methyl) acrylate | The double reactive compound | Hybrid system | Laminating | Membrane operations | Modulus (MPa) | Adhesive flow control | Tg (℃) | Peel adhesion (piw) | |
| ????1 | ????100 | ????82 | ????30 | ????0 | ????0 | ????HS | ????A | ????NT | ????NT | ????NT | ????165 | ????NT |
| ????2 | ????100 | ????91 | ????30 | ????8 | ????2 | ????LS | ????A | ????+ | ????1.2 | ????+ | ????165 | ????9.3 |
| ????3 | ????100 | ????91 | ????30 | ????12 | ????3 | ????LS | ????A | ????++ | ????5.3 | ????++ | ????161 | ????8.6 |
| ????4 | ????100 | ????82 | ????30 | ????16 | ????4 | ????LS | ????A | ????+++ | ????6.6 | ????++ | ????164 | ????8.3 |
| ????5 | ????100 | ????82 | ????30 | ????20 | ????5 | ????LS | ????A | ????+++ | ????15.0 | ????++ | ????157 | ????5.5 |
| ????6 | ????100 | ????82 | ????30 | ????24 | ????6 | ????LS | ????A | ????++ | ????15.1 | ????++ | ????149 | ????3.3 |
| ????7 | ????100 | ????82 | ????30 | ????57 | ????14 | ????HS | ????B | ????+ | ????86.4 | ????++ | ????148 | ????1.3 |
| ????8 | ????100 | ????82 | ????30 | ????73 | ????18 | ????HS | ????B | ????+ | ????237 | ????++ | ????158 | ????1.2 |
| ????9 | ????100 | ????91 | ????25 | ????8 | ????2 | ????LS | ????A | ????+ | ????NT | ????- | ????160 | ????9.2 |
| ????10 | ????100 | ????91 | ????25 | ????12 | ????3 | ????LS | ????A | ????+ | ????NT | ????+ | ????164 | ????8.8 |
| ????11 | ????100 | ????82 | ????25 | ????16 | ????4 | ????LS | ????A | ????++ | ????NT | ????+ | ????168 | ????7.1 |
| ????12 | ????100 | ????82 | ????25 | ????24 | ????6 | ????LS | ????A | ????++ | ????NT | ????+ | ????159 | ????3.4 |
| ????13 | ????100 | ????91 | ????20 | ????12 | ????3 | ????LS | ????A | ????- | ????NT | ????- | ????159 | ????8.8 |
| ????14 | ????100 | ????82 | ????20 | ????16 | ????4 | ????LS | ????A | ????+ | ????NT | ????+ | ????166 | ????7.5 |
| ????15 | ????100 | ????91 | ????20 | ????20 | ????5 | ????LS | ????A | ????++ | ????NT | ????+ | ????164 | ????3.5 |
| ????16 | ????100 | ????82 | ????20 | ????20 | ????5 | ????LS | ????A | ????++ | ????NT | ????+ | ????161 | ????5.4 |
| ????17 | ????100 | ????82 | ????20 | ????24 | ????6 | ????LS | ????A | ????+ | ????NT | ????+ | ????164 | ????4.2 |
NT=does not test
The data presentation of table 1 with about 5-20 part multifunctional (methyl) acrylate, 1-15 part double reactive compound and the benefit when the merging quantity of these materials is about 10-25 part (preferably about 15-20 part).When the merging quantity of multifunctional (methyl) acrylate and double reactive compound during, obtained especially good result for about 10-20 parts by weight.In the time of outside these scopes, peel adhesion and/or second-order transition temperature can descend.The Tg of embodiment 2-17 compares with the Tg of embodiment 1 (component that does not contain (methyl) acrylate) just better, this show the curable one-tenth of binder composition of the present invention Tg with basically based on the close material of Tg of the tackiness agent of aromatic polyepoxide.
Embodiment 18-20
In embodiment 18-20, veneer sheet is prepared and tests by the method for the foregoing description 1-17, and is shown in following table 2.Change the quantity of thermoplastic polymer, and the quantity of other reactive material remains unchanged.Embodiment 4,11 and 14 repeats to list in table 2.
Table 2
| Embodiment | Binder composition | Specimen preparation | Test result | ||||||||
| Aromatic polyepoxide | Solidifying agent | Thermoplastic polymer | Multifunctional (methyl) acrylate | The double reactive compound | Hybrid system | Laminating | Membrane operations | Adhesive flow control | Tg (℃) | Peel adhesion (piw) | |
| ?18 | ????100 | ??82 | ????0 | ????16 | ????4 | ??HS | ??B | ??- | ????- | ??169 | ????8.6 |
| ?19 | ????100 | ??82 | ????10 | ????16 | ????4 | ??LS | ??A | ??- | ????+ | ??162 | ????5.4 |
| ?20 | ????100 | ??82 | ????15 | ????16 | ????4 | ??LS | ??A | ??- | ????+ | ??167 | ????5.9 |
| ?14 | ????100 | ??82 | ????20 | ????16 | ????4 | ??LS | ??A | ??+ | ????+ | ??166 | ????7.5 |
| ?11 | ????100 | ??82 | ????25 | ????16 | ????4 | ??LS | ??A | ??++ | ????+ | ??168 | ????7.1 |
| ??4 | ????100 | ??82 | ????30 | ????16 | ????4 | ??LS | ??A | ??+++ | ????++ | ??164 | ????8.3 |
When table 2 has shown the quantity that increases thermoplastic polymer to the benefit of membrane operations and the adhesive flow control performance of tackiness agent bonding film.Preferably, tackiness agent bonding film of the present invention contains 20-40 part thermoplastic polymer of having an appointment, and is more preferably about 20-30 part.
Embodiment 21 and 22
In embodiment 21 and 22, veneer sheet is prepared and tests by the method for the foregoing description 1-17, and is shown in following table 3.Change the single quantity of multifunctional (methyl) acrylate and double reactive compound and merge quantity.And the quantity of aromatic polyepoxide and solidifying agent remains unchanged.The quantity of thermoplastic polymer is 0 or 30 part.Embodiment 4,7 and 8 repeats to list in table 3.
Table 3
| Embodiment | Binder composition | Specimen preparation | Test result | ||||||||
| Aromatic polyepoxide | Solidifying agent | Thermoplastic polymer | Multifunctional (methyl) acrylate | The double reactive compound | Hybrid system | Laminating | Membrane operations | Adhesive flow control | ??Tg ??(℃) | Peel adhesion (piw) | |
| ??4 | ????100 | ??82 | ????30 | ????16 | ????4 | ?LS | ??A | ??+++ | ??++ | ??164 | ??8.3 |
| ??7 | ????100 | ??82 | ????30 | ????57 | ????14 | ?HS | ??B | ??+ | ??++ | ??148 | ??1.3 |
| ??8 | ????100 | ??82 | ????30 | ????73 | ????18 | ?HS | ??B | ??+ | ??++ | ??158 | ??1.2 |
| ?21 | ????100 | ??82 | ????0 | ????49 | ????12 | ?HS | ??B | ??+ | ???- | ??171 | ??2.5 |
| ?22 | ????100 | ??82 | ????0 | ????64 | ????16 | ?HS | ??B | ??+ | ???- | ??168 | ??1.7 |
Table 3 shows, when the quantity of multifunctional (methyl) acrylate surpasses preferred 5-20 part scope, the quantity of optional double reactive compound surpasses preferred 1-15 part scope, and the merging quantity of these two kinds of materials is when surpassing preferred 10-25 part scope, and peel adhesion can descend and/or the adhesive flow increase in curing process.
Embodiment 23-25
In embodiment 23-25, be prepared and test by the method for the foregoing description 1-17, and be shown in following table 4.Difference is: (1) multifunctional (methyl) acrylate is replaced by following material: embodiment 23 (TEGDMA); Embodiment 24 (HDDA); With embodiment 25 (PhEMA), and (2) these materials not with the pre-mixing of double reactive compound, but the plastic cup described in the high-speed mixing method is put in separately weighing at room temperature, has contained aromatic polyepoxide/thermoplastic polymer mixtures before high-speed mixing begins in this cup.
Table 4
| Embodiment | Binder composition | Specimen preparation | Test result | ||||||||
| Aromatic polyepoxide | Solidifying agent | Thermoplastic polymer | (methyl) acrylate | The double reactive compound | Hybrid system | Laminating | Membrane operations | Adhesive flow control | Tg (℃) | Peel adhesion (piw) | |
| ?23 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ??B | ??++ | ????+ | 159 | ??8.4 |
| ?24 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ??B | ??++ | ????+ | 164 | ??1.9 |
| ?25 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ??B | ??- | ????- | 126 | ??NT |
NT=does not test
Table 4 shows, can use different multifunctional (methyl) acrylate in binder composition of the present invention and tackiness agent bonding film, although the peel adhesion that some multifunctional (methyl) acrylate provides is lower.In embodiment 25, multifunctional (methyl) acrylate is replaced by monofunctional acrylate, and this causes the lower and membrane operations decline of adhesive flow control.Tg also descends greatly.Peel adhesion in embodiment 25 does not have evaluated, because can't form effective veneer sheet specimen.
Embodiment 26 and 27
In embodiment 26 and 27, press method preparation and the test layer pressing plate of the foregoing description 1-17, and be shown in following table 5.Difference is: (1) D.E.R.
TM332 by EPON
TM828 replace and (2) PKHJ
TMReplaced by a thermoplastic polymer.This polymkeric substance contains EPON
TM828 and 75 weight %/25 weight % mixtures of P3500, its preparation is in 350 vigorous stirring at least 8 hours P3500 to be dissolved in EPON in mixing tank in enormous quantities
TM828.In embodiment 27, thermoplastic polymer is with extra EPON
TM828 dilutions are so that obtain this two kinds of ratios that component is required.
Embodiment 28-30
In embodiment 28-30, press method preparation and the test layer pressing plate of the foregoing description 1-17, and be shown in following table 5.Difference is: (1) D.E.R.
TM332 by QUATREX
TMThe method for making difference of 1010 replacements and (2) aromatic polyepoxide/thermoplastic polymer mixtures.In embodiment 28, PMMA thermoplastic polymer and aromatic polyepoxide are put into 8 ounces glass cylinder by weighing, place the convection of air stove of the preheating that is set in 130 ℃ then.Stir the mixture with wooden spatula by hand once in a while, until dissolving fully, sign is to form limpid uniform mixture.Allow mixture be cooled to room temperature.Mixture is not muddy after cooling, and this shows that PMMA still is dissolved in aromatic polyepoxide under room temperature.
In embodiment 29, thermoplastic polymer is Ultem
TM1000, and aromatic polyepoxide/thermoplastic polymer mixtures is muddy after being cooled to room temperature, this shows Ultem at room temperature
TM1000 are separated thereby no longer are dissolved in wherein with aromatic polyepoxide.
In embodiment 30 (method for making is with embodiment 28), thermoplastic polymer is PolyEMA, and aromatic polyepoxide/thermoplastic polymer mixtures is not muddy after cooling, and this shows that PolyEMA still is dissolved in aromatic polyepoxide under room temperature.
Embodiment 31
In embodiment 31, press method preparation and the test layer pressing plate of the foregoing description 1-17, and be shown in following table 5.Difference is: the method for making difference of aromatic polyepoxide/thermoplastic polymer mixtures.Thermoplastic polymer is Ultem
TM1000, it also is insoluble in the aromatic polyepoxide.Multifunctional (methyl) acrylate double reactive compound is mixed with the high-speed mixing method with aromatic polyepoxide.With Ultem
TMIn 1000 these mixtures of a collection of adding, mix with the high-speed mixing method then, until disperseing fully, its sign is not have the block or the particle of humidifying not.Add solidifying agent according to the high-speed mixing method.
Table 5
| Embodiment | Binder composition | Specimen preparation | Test result | ||||||||
| Aromatic polyepoxide | Solidifying agent | Thermoplastic polymer | Multifunctional (methyl) acrylate | The double reactive compound | Hybrid system | Laminating | Membrane operations | Adhesive flow control | ??Tg ??(℃) | Peel adhesion (piw) | |
| ?4 | ????100 | ??82 | ????30 | ????16 | ????4 | ?LS | ??A | ??+++ | ??++ | ??164 | ??8.3 |
| ?26 | ????100 | ??77 | ????25 | ????16 | ????4 | ?HS | ??B | ??++ | ??++ | ??160 | ??8.6 |
| ?27 | ????100 | ??77 | ????10 | ????16 | ????4 | ?HS | ??B | ???- | ???- | ??164 | ??4.5 |
| ?28 | ????100 | ??77 | ????30 | ????16 | ????4 | ?HS | ??B | ??++ | ???+ | ??149 | ??7.9 |
| ?29 | ????100 | ??77 | ????20 | ????16 | ????4 | ?HS | ??B | ???- | ???- | ??160 | ??5.3 |
| ?30 | ????100 | ??77 | ????30 | ????16 | ????4 | ?HS | ??B | ??+ | ???+ | ??163 | ??3.1 |
| ?31 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ??B | ??- | ???+ | ??156 | ??10.1 |
Embodiment 26 and 27 shows, when thermoplastic polymer is polysulfones, for high-performance needs bigger quantity.Embodiment 4 and 28 shows, uses the thermoplastic polymer of soluble, high Tg (between about 90-200 ℃) that good performance can be provided, and the thermoplastic polymer of low Tg (being lower than about 90 ℃) produces the low veneer sheet of peel adhesion among the embodiment 30.
Embodiment 29 shows that dissolving earlier still can cause low peel adhesion, the membrane operations and the controlled reduction of adhesive flow of difference in case be cooled to the thermoplastic polymer that is separated after the room temperature.It is preferable that thermoplastic polymer is dissolved in binder composition all the time.
Embodiment 31 shows, has with dispersive, the thermoplastic polymer that exists of solubilized form can not reduce the operability of tackiness agent bonding film, but still has high peel adhesion and high Tg.
Embodiment 32 and 33
In embodiment 32 and 33, press method preparation and the test layer pressing plate of the foregoing description 1-17, and be shown in following table 6.Difference is: the CAF solidifying agent is replaced by CG-1400 in embodiment 32, in embodiment 33 by D.E.H.
TM85 replace.
Table 6
| Embodiment | Binder composition | Specimen preparation | Test result | ||||||||
| Aromatic polyepoxide | Solidifying agent | Thermoplastic polymer | Multifunctional (methyl) acrylate | The double reactive compound | Hybrid system | Laminating | Membrane operations | Adhesive flow control | ??Tg ??(℃) | Peel adhesion (piw) | |
| ?32 | ????100 | ????6 | ????30 | ????16 | ????4 | ????HS | ????B | ????++ | ????++ | ????NO | ????10.1 |
| ?33 | ????100 | ????87 | ????30 | ????16 | ????4 | ????HS | ????B | ????- | ????- | ????99 | ????NT |
NO=does not observe
NT=does not test
Embodiment 32 shows that the solidifying agent except that aromatic amine can be used for binder composition of the present invention and tackiness agent bonding film.Yet, the binder composition that the phenol type solidifying agent that uses in embodiment 33 forms, wherein multifunctional (methyl) acrylate and the not polymerization of double reactive compound when being exposed to electron beam irradiation.In embodiment 33, do not assess peel adhesion, because can't form effective veneer sheet specimen.
Embodiment 34-38
In embodiment 34-38, press method preparation and the test layer pressing plate of the foregoing description 1-17, and be shown in following table 8.Difference is: EBECRYL 3605 double reactive compounds are replaced by (methyl) acrylate of the various simple functions in the table 7.
Table 7
| Embodiment | (methyl) acrylate of simple function |
| ????34 | ????PhEMA |
| ????35 | ????IBMA |
| ????36 | ????IBA |
| ????37 | ????PEA |
| ????38 | ????THFA |
Table 8
| Embodiment | Binder composition | Specimen preparation | Test result | ||||||||
| Aromatic polyepoxide | Solidifying agent | Thermoplastic polymer | Multifunctional (methyl) acrylate | Simple function (methyl) acrylate | Hybrid system | Laminating | Membrane operations | Adhesive flow control | Tg (℃) | Peel adhesion (piw) | |
| ?34 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ??B | ??+ | ????+ | 159 | ????3.2 |
| ?35 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ??B | ??+ | ????+ | 165 | ????2.0 |
| ?36 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ??B | ??++ | ????+ | 166 | ????3.1 |
| ?37 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ??B | ??++ | ????- | 166 | ????2.0 |
| ?38 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ??A | ??++ | ????- | 153 | ????1.9 |
Table 8 shows that the double reactive compound is not must be included in the binder composition of the present invention.Although be the component of choosing wantonly, exist the double reactive compound still very favourable, because it can advantageously influence the controlled and/or peel adhesion of adhesive flow of tackiness agent bonding film.
Embodiment 39 and 40
Prepare binder composition by top " the general preparation method of binder composition " described method of part, wherein prescription is listed in the table below in 9.Embodiment 39 and 40 also contains ultraviolet ray (UV) the radio polymerization initiator DAROCUR of 2% (w/w is calculated by the merging quantity of multifunctional (methyl) acrylate and double reactive compound)
TM1173 (Ciba Geigy, Inc., Hawthorne, NY).In addition, in case binder composition is applied between two release liner, just replace electron beam irradiation to carry out polymerization with the UV radiation.
More specifically, in embodiment 39, under the condition of no oxygen, with RPG UV Processor (the Model QC 1202AN that 2 high strength mercury lamps (emission maximum is 365 nanometers) are housed
3IR, from PPG Industries, Inc., Plainfield, IL) tackiness agent after will applying is exposed under the UV radiation of high energy.One side is exposed 9 times, and each 4.6 seconds, average intensity was 57.83mW/cm
2, total UV exposure energy is 2394mJ/cm
2Intensity is with UVIRAD UV Integrating Radiometer (Model UR
365CH
3, from Electronic Instrumentation﹠amp; Technology, Sterling Virginia) measures, and is converted into National Institute of Standards andTechnology (NIST) unit (listing in herein).
In embodiment 40, under the condition of no oxygen, use Sylvania
TMLuminescent lamp (its 90% be transmitted between the 300-400 nanometer, maximum value is in 351 nanometers) is exposed under the low-energy UV radiation tackiness agent of coating.Every side is exposed 20 minutes, and average intensity is 2.045mW/cm
2/ side, total UV exposure energy is 2451mJ/cm
2/ side.As above measured intensity.
Table 9
| Embodiment | Binder composition | Specimen preparation | Test result | ||||||||
| Aromatic polyepoxide | Solidifying agent | Thermoplastic polymer | Multifunctional (methyl) acrylate | The double reactive compound | Hybrid system | Laminating | Membrane operations | Adhesive flow control | ??Tg ??(℃) | Peel adhesion (piw) | |
| ?39 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ?A | +++ | ????++ | ??164 | ??9.0 |
| ?40 | ????100 | ??82 | ????30 | ????16 | ????4 | ?HS | ?A | +++ | ????++ | ??162 | ??9.3 |
Table 9 shows that although can produce useful tackiness agent and tackiness agent bonding film with the UV radiation, electron beam irradiation used according to the invention is more effective.Total radiation exposure duration of embodiment 39 is 41 seconds, and is 40 minutes among the embodiment 40.Yet the electron beam irradiation that only used 0.5 second in other embodiment of preparation exposes.
Repeat embodiment 39 and 40, just do not add light trigger.The controlled grade of membrane operations and adhesive flow is negative (-); Other performances are not measured.After being exposed to the UV radiation, be dissolved in the methylethylketone at once among the multiple embodiment, this shows that binder composition of the present invention does not have abundant polymerization and crosslinked when being exposed to the UV radiation, thereby needs special storage and packing (as in light tightization radiating container).
Embodiment 41-46
In embodiment 41-46, press method preparation and the test layer pressing plate of the foregoing description 1-17, and be shown in following table 10.Difference is: multifunctional (methyl) acrylate and double reactive compound are not pre-mixed among the embodiment 46, because do not contain the double reactive compound among this embodiment.
Table 10
| Embodiment | Binder composition | Specimen preparation | Test result | |||||||||
| Aromatic polyepoxide | Solidifying agent | Thermoplastic polymer | Multifunctional (methyl) acrylate | The double reactive compound | Multi-functional (methyl) acrylate: the ratio of double reactive compound | Hybrid system | Laminating | Membrane operations | Adhesive flow control | Tg(℃) | Release adhesive (piw) | |
| ?41 | ????100 | ????82 | ????30 | ????20 | ????0 | ????100∶0 | ????HS | ????A | ????+++ | ????+ | ????167 | ????2.5 |
| ?42 | ????100 | ????82 | ????30 | ????19 | ????1 | ????95∶5 | ????HS | ????A | ????+++ | ????+ | ????164 | ????4.2 |
| ?4 | ????100 | ????82 | ????30 | ????16 | ????4 | ????80∶20 | ????LS | ????A | ????+++ | ????++ | ????164 | ????8.3 |
| ?43 | ????100 | ????82 | ????30 | ????15 | ????5 | ????75∶25 | ????HS | ????A | ????++ | ????++ | ????161 | ????8.5 |
| ?44 | ????100 | ????82 | ????30 | ????10 | ????10 | ????50∶50 | ????HS | ????A | ????++ | ????++ | ????158 | ????8.3 |
| ?45 | ????100 | ????82 | ????30 | ????13 | ????13 | ????50∶50 | ????HS | ????A | ????+++ | ????++ | ????158 | ????8.8 |
| ?46 | ????100 | ????82 | ????25 | ????0 | ????20 | ????0∶100 | ????LS | ????A | ????+ | ????- | ????165 | ????9.0 |
Table 10 has shown the effect when changing multifunctional (methyl) acrylate to the ratio of double reactive compound.Example in 80: 20 to 50: 50 the proportional range demonstrates excellent performance.When ratio exceeded this scope, peel adhesion can descend.Multifunctional (methyl) acrylate can change between 95: 5 to 50: 50 on a large scale to the ratio of double reactive compound.Embodiment 45 has multifunctional (methyl) acrylate and the double reactive compound that merges quantity 25 parts by weight, and it shows good performance.
Embodiment 47-49
In embodiment 47-49, press method preparation and the test layer pressing plate of the foregoing description 1-17, and be shown in following table 11, but some difference is arranged.Each embodiment comprises 9 part six-(4-methoxyl group-phenoxy group) ring three phosphazo-alkene (cyclotriphosphazene) fire retardants and 6 parts of ARACAST among the embodiment 47-49
TMXU AY238 epoxy glycolylurea.Fire retardant is dissolved in aromatic polyepoxide/thermoplastic polymer mixtures, and then the epoxy glycolylurea is dissolved in this mixture.In each these embodiment, aromatic polyepoxide is the D.E.R. of identical weight umber
TM332 and the mixture of D.E.N.438.Double reactive compound in each embodiment is SARTOMER 379.
In embodiment 48 and 49, the preheating in being set in 100 ℃ convection of air stove of aromatic polyepoxide/thermoplastic polymer mixtures until reaching dumpable viscosity, joins Plastic-corder then
TMIn the PL-2000 mixing tank, this mixing tank is set to 65 ℃ in embodiment 48, is set to 70 ℃ in embodiment 49.
Table 11
| Embodiment | Binder composition | Specimen preparation | Test result | ||||||||
| Aromatic polyepoxide | Solidifying agent | Thermoplastic polymer | Multifunctional (methyl) acrylate | The double reactive compound | Hybrid system | Laminating | Membrane operations | Adhesive flow control | ??Tg ??(℃) | Release adhesive (piw) | |
| ?47 | ????100 | ??89 | ????20 | ????17 | ????4 | ?LS | ?A | ??++ | ??++ | ??172 | ??8.1 |
| ?48 | ????100 | ??89 | ????30 | ????17 | ????4 | ?LS | ?A | ??+++ | ??+++ | ??172 | ??8.3 |
| ?49 | ????100 | ??89 | ????40 | ????17 | ????4 | ?LS | ?A | ??+++ | ??+++ | ??174 | ??8.4 |
Table 11 shows, can use the mixture of different aromatic polyepoxides in binder composition of the present invention and tackiness agent bonding film, also can use glycidyl methacrylate double reactive compound and various fire retardants.
In scope and spirit of the present invention, it is conspicuous for a person skilled in the art that various change of the present invention and version are arranged.Should be understood that the present invention is not limited thereto locates illustrative example.
Claims (37)
1. binder composition solvent-free, that light is stable is characterized in that it contains:
A) aromatic polyepoxide;
B) the hot activation solidifying agent of polyepoxide;
C) thermoplastic polymer;
D) polyfunctional (methyl) acrylate; With
E) compound of Ren Xuan double reactive, it contain at least one (methyl) acrylate group and at least one can with the group of aromatic polyepoxide reaction.
2. solvent-free, binder composition that light is stable as claimed in claim 1 is characterized in that the second-order transition temperature of this thermoplastic polymer is about 90-200 ℃.
3. solvent-free, binder composition that light is stable as claimed in claim 1 is characterized in that, the number-average molecular weight of this thermoplastic polymer is about 10,000-100,000.
4. solvent-free, binder composition that light is stable as claimed in claim 1 is characterized in that this thermoplastic polymer is selected from down group: the mixture of polysulfones, poly-(methyl methacrylate), phenoxy group polymkeric substance, polycarbonate and these materials.
5. solvent-free, binder composition that light is stable as claimed in claim 1 is characterized in that this thermoplastic polymer is about 20-40 parts by weight, by 100 parts by weight aromatic polyepoxides.
6. solvent-free, binder composition that light is stable as claimed in claim 1 is characterized in that this multifunctional (methyl) acrylate is two (methyl) acrylate.
7. solvent-free, binder composition that light is stable as claimed in claim 1 is characterized in that this multifunctional (methyl) acrylate is about 5-20 parts by weight, by 100 parts by weight aromatic polyepoxides.
8. solvent-free, binder composition that light is stable as claimed in claim 1 is characterized in that, has this double reactive compound, and it is about 1-15 parts by weight, by 100 parts by weight aromatic polyepoxides.
9. solvent-free, binder composition that light is stable as claimed in claim 1, it is characterized in that, there is this double reactive compound, and the merging quantity of multifunctional (methyl) acrylate and double reactive compound is about 10-25 parts by weight, by 100 parts by weight aromatic polyepoxides.
10. solvent-free, binder composition that light is stable as claimed in claim 1, it is characterized in that, multifunctional when being exposed to electron beam irradiation (methyl) acrylate and optional double reactive compound can polymerizations, and wherein the hot activation solidifying agent of aromatic polyepoxide and polyepoxide does not react when being exposed to electron beam irradiation.
11. solvent-free, binder composition that light is stable as claimed in claim 1 is characterized in that, its viscosity can apply this binder composition under the temperature of the temperature of reaction of the hot activation solidifying agent that is lower than polyepoxide.
12. solvent-free, binder composition that light is stable as claimed in claim 11 is characterized in that, this binder composition can apply being lower than under about 90 ℃ temperature.
13. solvent-free, binder composition that light is stable as claimed in claim 1, it is characterized in that aromatic polyepoxide, thermoplastic polymer, multifunctional (methyl) acrylate and optional double reactive compound at room temperature provide with the solution form
14. solvent-free, as to be substantially free of a photoresponse material binder composition is characterized in that this binder composition contains:
A) aromatic polyepoxide of 100 parts by weight;
B) the hot activation solidifying agent of the polyepoxide of curing significant quantity;
C) thermoplastic polymer of about 20-40 parts by weight, this thermoplastic polymer is selected from down group: the mixture of polysulfones, poly-(methyl methacrylate), phenoxy group polymkeric substance, polycarbonate and these materials;
D) two of about 5-20 parts by weight (methyl) acrylate; With
E) a kind of compound of about 1-15 parts by weight, it contains at least one (methyl) acrylate group and at least one is selected from down the group of group: hydroxyl, carboxyl, amido and 1,2-epoxy group(ing).
15. solvent-free binder composition as claimed in claim 14 is characterized in that, it is to have the solution that can apply viscosity when being less than or equal to about 90 ℃ temperature.
16. solvent-free binder composition as claimed in claim 14 is characterized in that, it contains the thermoplastic polymer of the 20-30 parts by weight of having an appointment.
17. solvent-free binder composition as claimed in claim 14 is characterized in that, the merging quantity of component (d) and component (e) is about 15-20 parts by weight.
18. a heat-setting tackiness agent bonding film is characterized in that it contains
A) heat-setting aromatic polyepoxide;
B) the hot activation solidifying agent of polyepoxide;
C) thermoplastic polymer; With
D) (methyl) acrylic ester polymer net, it is the electron beam irradiation polymerisate of following component:
1) polyfunctional (methyl) acrylate; With
2) Ren Xuan a kind of compound, it contain at least one (methyl) acrylate group and at least one can with the group of aromatic polyepoxide reaction.
19. heat-setting tackiness agent bonding film as claimed in claim 18 is characterized in that it is placed on the area supported.
20. heat-setting tackiness agent bonding film as claimed in claim 19 is characterized in that this area supported is provisional carrier.
21. heat-setting tackiness agent bonding film as claimed in claim 19 is characterized in that this area supported is permanent backing.
22. heat-setting tackiness agent bonding film as claimed in claim 18 is characterized in that it can take off from provisional carrier, and fold does not take place, tears or nonvolatil stretching.
23. heat-setting tackiness agent bonding film as claimed in claim 18 is characterized in that its modulus is about 1-300MPa.
24. heat-setting tackiness agent bonding film as claimed in claim 18 is characterized in that it shows controlled adhesive flow in curing process.
25. heat-setting tackiness agent bonding film as claimed in claim 18 is characterized in that it is by thermofixation.
26. the tackiness agent bonding film of thermofixation as claimed in claim 25 is characterized in that, its second-order transition temperature is at least about 150 ℃.
27. fibre-reinforced heat-setting tackiness agent bonding film as claimed in claim 18.
28. a heat-setting tackiness agent bonding film is characterized in that it contains
A) the heat-setting aromatic polyepoxide of 100 parts by weight;
B) the hot activation solidifying agent of the polyepoxide of curing significant quantity;
C) thermoplastic polymer of about 20-40 parts by weight, this thermoplastic polymer is selected from down group: the mixture of polysulfones, poly-(methyl methacrylate), phenoxy group polymkeric substance, polycarbonate and these materials; With
D) (methyl) acrylic ester polymer net, it is the electron beam irradiation polymerisate of following component:
1) about 5-20 parts by weight two (methyl) acrylate; With
2) a kind of compound of about 1-15 parts by weight, it contains at least one (methyl) acrylate group and at least one is selected from down the group of group: hydroxyl, carboxyl, amido and 1,2-epoxy group(ing).
29. heat-setting tackiness agent bonding film as claimed in claim 28 is characterized in that it can take off from provisional carrier, and fold does not take place, tears or nonvolatil stretching.
30. heat-setting tackiness agent bonding film as claimed in claim 29 is characterized in that its modulus is about 1-300MPa.
31. a printed circuit board (PCB) is characterized in that, it contains by the as claimed in claim 28 heat-setting tackiness agent bonding film of thermofixation.
32. a method for preparing the tackiness agent bonding film is characterized in that the method comprising the steps of:
A) provide a kind of binder composition, said composition contains
1) heat-setting aromatic polyepoxide;
2) the hot activation solidifying agent of polyepoxide;
3) thermoplastic polymer;
4) polyfunctional (methyl) acrylate; With
5) compound of Ren Xuan double reactive, it contain at least one (methyl) acrylate group and at least one can with the group of aromatic polyepoxide reaction;
B) on area supported, form this adhesive composition layer;
C) adhesive composition layer is exposed to electron beam irradiation, with polymerization multifunctional (methyl) acrylate and optional double reactive compound, but do not cause the reaction of hot activation solidifying agent or aromatic polyepoxide, thereby form heat-setting tackiness agent bonding film.
33. method as claimed in claim 31 is characterized in that, curable aromatic polyepoxide, thermoplastic polymer, multifunctional (methyl) acrylate and optional double reactive compound form solution in step (a).
34. method as claimed in claim 32 is characterized in that, the formation of adhesive composition layer be by: under the temperature between about room temperature to 120 ℃, binder composition is coated on the area supported.
35. method as claimed in claim 33 is characterized in that, binder composition is to apply under the temperature between about room temperature to 60 ℃.
36. method as claimed in claim 32 is characterized in that, also comprises step: heat-setting tackiness agent bonding film is taken off from area supported, and heat-setting tackiness agent bonding film fold does not take place, tears or nonvolatil stretching.
37. method as claimed in claim 32 is characterized in that, also comprises step: heat heat-setting tackiness agent bonding film for some time at a certain temperature, make it be enough to solidify aromatic polyepoxide, thereby form the tackiness agent bonding film of thermofixation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96194955A CN1188501A (en) | 1995-06-21 | 1996-06-05 | Adhesive compositions, bonding films made therefrom and processes for making bonding films |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/493,263 | 1995-06-21 | ||
| CN96194955A CN1188501A (en) | 1995-06-21 | 1996-06-05 | Adhesive compositions, bonding films made therefrom and processes for making bonding films |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1188501A true CN1188501A (en) | 1998-07-22 |
Family
ID=5128923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96194955A Pending CN1188501A (en) | 1995-06-21 | 1996-06-05 | Adhesive compositions, bonding films made therefrom and processes for making bonding films |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1188501A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353837A (en) * | 2016-04-28 | 2017-11-17 | 利诺士尖端材料有限公司 | Non-conductive cohesive film composition and the non-conductive adhesive film for including it |
-
1996
- 1996-06-05 CN CN96194955A patent/CN1188501A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353837A (en) * | 2016-04-28 | 2017-11-17 | 利诺士尖端材料有限公司 | Non-conductive cohesive film composition and the non-conductive adhesive film for including it |
| CN107353837B (en) * | 2016-04-28 | 2020-12-29 | 利诺士尖端材料有限公司 | Composition for non-conductive adhesive film and non-conductive adhesive film comprising same |
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