EP1053280A1 - Composition adhesive et son precurseur - Google Patents

Composition adhesive et son precurseur

Info

Publication number
EP1053280A1
EP1053280A1 EP99902053A EP99902053A EP1053280A1 EP 1053280 A1 EP1053280 A1 EP 1053280A1 EP 99902053 A EP99902053 A EP 99902053A EP 99902053 A EP99902053 A EP 99902053A EP 1053280 A1 EP1053280 A1 EP 1053280A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
adhesive composition
resin
epoxy resin
antimony pentaoxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99902053A
Other languages
German (de)
English (en)
Inventor
Kohichiro Kawate
Yuji Hiroshige
Hitoshi Yamaguchi
Akito Muramatsu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP1053280A1 publication Critical patent/EP1053280A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/54—Inorganic substances
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils

Definitions

  • the present invention relates to an adhesive composition having improved noncombustibility.
  • the present invention also relates to an adhesive precursor composition useful as a starting material for the adhesive composition. Description of the Related Art
  • a film formed of an adhesive composition comprising a combination of various thermoplastic resins with an epoxy resin as a thermosetting resin is used as an adhesive film for protecting FPC (flexible printed circuitor wiring board) (see, for example, Japanese Unexamined Patent Publication (Kokai) Nos. 9-132710, 9-125037, 5-5085, 3-6280, 2-145676, 62274690, 60-130666, 1-135844, and 61-43550).
  • an adhesive film formed of a composition comprising a phenoxy resin, an epoxy resin, and a curing agent possesses heat resistance, adhesion to metallic parts and other properties and hence has been regarded as useful in the art.
  • a dicyandiamide has been used as the curing agent because of its potential for curability.
  • polyester resins and various elastomers are disclosed to be usable as the thermoplastic resin.
  • the adhesive composition according to the above formulation (the adhesive composition composed mainly of a phenoxy resin, an epoxy resin, and a dicyandiamide curing agent), however, has low non-combustibility and, in particular, cannot satisfy the non-combustibility requirement (NO) specified in UL standards.
  • addition of brominated epoxy resin in combination with antimony pentaoxide to improve the noncombustibility of the resin compositions is a method known in the art.
  • This method comprises mixing an antimony pentaoxide powder with the resin component to form a non-combustible composition.
  • An antimony pentaoxide powder is relatively inexpensive and can contribute to a lowering in product price in addition to an improvement in non-combustibility. Due to the size of the powder, however, it has a problem.
  • the antimony pentaoxide powder since the average particle diameter of the antimony pentaoxide powder is generally not less than 0.5 gm, the antimony pentaoxide powder is likely to settle by gravity in a mixed liquid composed of an effective amount of the antimony pentaoxide powder, a resin component, and a solvent, making it difficult to prepare a composition wherein the components are intimately mixed with one another. Heterogeneous dispersion of the components in the adhesive composition leads to deteriorated adhesive strength and dimensional stability and unfavorably results in remarkably deteriorated properties as an adhesive for the adhesive film for protection of FPC.
  • an adhesive composition which contains antimony pentaoxide, in a dispersed state, in an amount necessary for satisfying the NO requirement (in general, not less than 3 % by weight based on the whole composition) while enjoying excellent adhesive properties (such as adhesive properties and dimensional stability) and further contains a phenoxy resin, an epoxy resin, and a curing agent, has never been known in the art.
  • the present invention provides an adhesive composition, comprising a phenoxy resin, an epoxy resin, and a curing agent, which possesses non-combustibility good enough to pass the VO requirement and excellent adhesive performance (such as adhesive properties and dimensional stability) as an adhesive for an adhesive film for an FPC protection film.
  • the present invention also provides an adhesive composition precursor useful as a starting material for such an excellent adhesive composition.
  • an adhesive composition containing a resin component, the resin component comprising a phenoxy resin, an epoxy resin, and a dicyandiamide, the epoxy resin comprising a brominated epoxy resin, the resin component containing colloidal particles of antimony pentaoxide
  • the total amount of the brominated epoxy resin and the colloidal particles of antimony pentaoxide being in the range of 13 to 60% by weight based on the total amount of the adhesive composition.
  • an adhesive composition precursor which, after drying, provides the above adhesive composition
  • the adhesive composition precursor comprising a mixture of (i) the resin component, (ii) an antimony pentaoxide sol comprising a dispersing medium, containing methyl ethyl ketone, and dispersed in the dispersing medium, the colloidal particles of antimony pentaoxide, and (iii) a solvent containing methanol, the weight ratio of methanol (MEOH) to methyl ethyl ketone (MEK) in the mixture, MeOH/MEK, being in the range of 0.005 to 0.4.
  • MEOH methanol
  • MEK methyl ethyl ketone
  • the adhesive composition of the present invention is a composition comprising a resin component, the resin component comprising a phenoxy resin, an epoxy resin, and a dicyandiamide as a curing agent, wherein the brominated epoxy resin and the colloidal particles of antimony pentaoxide (hereinafter often referred to as "antimony pentaoxide particles) are contained in the above specific proportion, that is, so that the total amount of the brominated epoxy resin and the colloidal particles of antimony pentaoxide is in the range of 13 to 60% by weight based on the total amount of the adhesive composition.
  • the adhesive composition When the total amount of the brominated epoxy resin and the antimony pentaoxide particles is less than 13% by weight based on the whole adhesive composition, the adhesive composition generally does not satisfy the V0 requirement. On the other hand, when it exceeds 60% by weight, the adhesive strength may be lowered. For example, when use of the adhesive composition as an adhesive for an adhesive film for protection of
  • resin component refers to a mixture composed of a phenoxy resin, an epoxy resin, a dicyandiamide, and optionally an additional components and containing neither a solvent nor inorganic particles. Suitable additional components
  • the epoxy resin may comprise either a brominated epoxy resin alone or a mixture of a brominated epoxy resin with a non-brominated epoxy resin.
  • brominated epoxy resin used herein refers to an epoxy resin with a bromine atom introduced into the molecule, for example, one having such a structure that one or more hydrogen atoms on a benzene ring within the molecule of a bisphenol type epoxy resin has been substituted by a bromine atom.
  • an epoxy resin other than the "brominated epoxy resin” is expressly defined as "non-brominated epoxy resin.”
  • the antimony pentaoxide particles are contained in the form of colloidal particles, the antimony pentaoxide particles do not settle by gravity in the dispersion containing the antimony pentaoxide particles and can be stably dispersed. Therefore, in the adhesive composition of the present invention prepared by drying this type of a dispersion can realize such a state that the components have been intimately mixed with one another, enabling the adhesive strength and the dimensional stability to be effectively improved.
  • the "colloidal particles of antimony pentaoxide” are generally fine particles of antimony pentaoxide having an average particle diameter in the range of 1 to 100 nm.
  • an antimony pentaoxide sol is mixed with the resin component so that the colloidal particles are contained in a dispersed state in the resin component.
  • the content of the antimony pentaoxide is generally not less than 3% by weight, preferably not less than 4% by weight, particularly preferably not less than 5% by weight based on the whole adhesive composition.
  • an adhesive composition precursor comprising a mixture of: a resin component comprising a phenoxy resin, an epoxy resin, and a dicyandiamide as a curing agent; an antimony pentaoxide sol comprising colloidal particles of antimony pentaoxide; and optionally a solvent, is suitable as a starting material for the above
  • this adhesive composition precursor contains antimony pentaoxide particles as the antimony pentaoxide sol, a stably dispersed state can be easily realized. Further, the content of the antimony pentaoxide particles can be easily increased, for example, to not less than about 5% by weight based on the whole adhesive composition with satisfactory results.
  • a precursor suitable as the above adhesive composition precursor comprises a mixture of (i) the resin component, (ii) an antimony pentaoxide sol comprising a dispersing medium, containing methyl ethyl ketone, and dispersed in the dispersing medium, the colloidal particles of antimony pentaoxide, and (iii) a solvent containing methanol, the weight ratio of methanol (MEOH) to methyl ethyl ketone (MEK) in the mixture, MeOH/MEK, being in the range of 0.005 to 0.4.
  • an antimony pentaoxide sol comprising a dispersing medium, containing methyl ethyl ketone, and dispersed in the dispersing medium, the colloidal particles of antimony pentaoxide
  • a solvent containing methanol the weight ratio of methanol (MEOH) to methyl ethyl ketone (MEK) in the mixture, MeOH/MEK, being in the range of 0.005
  • the dicyandiamide can be dissolved in only limited solvents, and, in many cases, resins, such as phenoxy resin and epoxy resin, are sparingly soluble in good solvents for the dicyandiamide. Therefore, in the adhesive composition prepared by drying the liquid containing the resin component and the antimony pentaoxide particles, the selection of the kind of the solvent is important for the formation of the above homogeneous dispersion structure.
  • a mixed solvent composed of methyl ethyl ketone, dimethylformamide, and methyl cellosolve is useful as the above solvent.
  • the present inventors have actually confirmed that a solid composition prepared by drying a mixed liquid composed of the mixed solvent and the above resin component (comprising a phenoxy resin, an epoxy resin, and a dicyandiamide) can develop a homogeneous structure capable of realizing good adhesive properties and dimensional stability because the dicyandiamide, after it is once dissolved, is precipitated as a fine crystal.
  • dimethylformamide and methyl cellosolve have low evaporation rate, and drying at a relatively low temperature for a relatively short period of time causes dimethylformamide and methyl cellosolve to remain unremoved in a relatively large amount in the composition after the drying.
  • the residual amount of dimethylformamide and the residual amount of methyl cellosolve were respectively 33 ⁇ g and 13 ⁇ g per g of the composition after drying.
  • the resultant solvent when the composition is used as an adhesive, creates foaming or soiling of the adherend. Therefore, preferably, the amount of the resultant solvent should be reduced as much as possible. Further, there is a possibility that the residual solvent is an obstacle to an improvement in adhesion and dimensional stability.
  • the adhesive composition precursor of the present invention only methyl ethyl ketone and methanol are used as the solvent, and the above solvent having low evaporation rate is not used. Therefore, even drying at a relatively low temperature for a relatively short period of time hardly causes the solvent to remain unremoved.
  • the mixed solvent composed of methyl ethyl ketone and methanol has high evaporation rate and, at the same time, has excellent capability of dissolving the above resin component and offers excellent dispersion stability of antimony pentaoxide particles.
  • the weight ratio of methanol (MeOH) to methyl ethyl ketone (MEK), MeOH/MEK is in the range of 0.005 to 0.4.
  • the selection of the above mixing ratio in the mixed solvent is effective in enhancing the capability of dissolving the resin component and the dispersion stability of antimony pentaoxide particles. Therefore, intimate mixing of the components with one another can be easily realized, and the amount of the residual solvent can be minimized.
  • methanol has a remarkably low capability of dissolving the phenoxy resin.
  • addition of the brominated epoxy resin increases the compatibility region in the mixed solvent composed of methyl ethyl ketone and methanol.
  • the resin component contained in the adhesive composition of the present invention generally comprises the following components: (a) a phenoxy resin, (b) a non-brominated epoxy resin,
  • the resin component comprises, based on the whole resin component, 40 to 90% by weight of the component (a), 4 to 30% by weight of the component (b), 4 to 50% by weight of the component (c), and 0.1 to 7% by weight of the component (d).
  • the resin component comprises, based on the whole resin component, 50 to 87% by weight of the component (a), 5 to 20% by weight of the component (b), 5 to 40% by weight of the component (c), and 0.5 to 5% by weight of the component (d).
  • the phenoxy resin as the component (a) is one of the components which contribute to an improvement in adhesive strength of the composition.
  • the intermolecular force, between the hydroxyl group of the polymer molecule constituting the phenoxy resin and the surface of the adherend, and the flexibility inherent in the resin mainly contribute to an improvement in adhesive strength in terms of peel strength.
  • the kind and the amount of the phenoxy resin added are selected so that the glass transition temperature of the cured composition is not 70°C or below. This results in enhanced dynamic folding resistance of the cured composition and hence can effectively prevent breaking or separation of the adhesive layer during use.
  • the non-brominated epoxy resin as the component (b) functions to enhance the glass transition temperature of the cured composition through a reaction thereof with a
  • the high glass transition temperature is advantageous in enhancing the dimensional stability and the heat resistance.
  • the kind and the amount of the non-brominated epoxy resin added are selected so that the glass transition temperature of the cured composition is not 70°C or below.
  • Non- brominated epoxy resins usable herein include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin and the like. Although the non-brominated epoxy resin is not an indispensable component, incorporation thereof is preferred from the viewpoint of enhancing the adhesive strength.
  • the brominated epoxy resin as the component (c) functions to enhance the noncombustibility of the composition and to enhance the solubility of the phenoxy resin in the mixed solvent composed of methyl ethyl ketone and methanol. Further, the brominated epoxy resin exhibits the same function as the non-brominated epoxy resin through a reaction thereof with the dicyandiamide.
  • the kind and the amount of the brominated epoxy resin added are selected so that the noncombustibility of the composition, the solubility of the phenoxy resin, and the glass transition temperature (above 70°C) of the composition are balanced.
  • Brominated epoxy resins usable herein include, for example, a bromination product of bisphenol A type epoxy resin.
  • the dicyandiamide as the component (d) is a curing agent for the components (b) and (c).
  • the term "dicyandiamide” used herein embraces both dicyandiamide and a dicyandiamide derivative.
  • the kind and the amount of the dicyandiamide added also are selected in the same manner as described above in connection with the other components constituting the resin component.
  • the resin component may comprise, in addition to the components (a) to (d), other additional components.
  • the amount of the additional components is selected in the same manner as described above in connection with the above other components constituting the resin component.
  • Adhesive composition precursor Adhesive composition precursor
  • the adhesive composition precursor is a starting material, for an adhesive composition, which, after drying, provides the adhesive composition of the present invention.
  • This precursor generally comprises the above resin component, colloidal particles of antimony pentaoxide, and a solvent.
  • the antimony pentaoxide particles are generally mixed as a sol with the above other components.
  • the antimony pentaoxide sol generally comprises antimony pentaoxide particles dispersed in an organic solvent.
  • the solvent for the sol is selected by taking into consideration the solubility of the resin component therein.
  • methyl ethyl ketone is preferred as the solvent. This is because methyl ethyl ketone has a good capability of dissolving the resin component and, in addition, is not detrimental to the dispersion stability of the sol (particles) in the precursor.
  • the concentration of the antimony pentaoxide is generally in the range of 5 to 50% by weight.
  • a mixed solvent containing methyl ethyl ketone and methanol is suitably used as the solvent.
  • the solvent may contain other solvents, for example, alcohols such as ethanol, isopropyl alcohol, npropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tbutyl alcohol and the like, nitrogen-containing solvents such as acetonitrile and the like, and others.
  • alcohols such as ethanol, isopropyl alcohol, npropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tbutyl alcohol and the like, nitrogen-containing solvents such as acetonitrile and the like, and others.
  • ethanol exhibits a good solubility in dicyandiamide, shows a lower evaporation rate than that of methyl ethyl ketone, and does not remarkably reduce an evaporation rate of the mixed solvent. Accordingly, ethanol can effectively improve a uniformity of the coating without reducing
  • the above resin component is first mixed with the above solvent to prepare a homogeneous solution.
  • suitable mixing means include a high speed mixer, a planetary mixer, a homomixer, and a sand mill.
  • the concentration of the resin solution is generally in the range of 5 to 70% by weight.
  • the antimony pentaoxide sol is added to and mixed with the resin component solution by mixing means to prepare a dispersion, thereby preparing an adhesive composition precursor comprising the dispersion.
  • a precursor containing antimony pentaoxide particles homogeneously stably dispersed in the above resin component can be easily prepared.
  • Mixing of the resin component solution with the antimony pentaoxide sol may be carried out by the same means as described above.
  • the adhesive composition precursor may comprise various additives so far as these additives are not detrimental to the effect of the present invention.
  • Suitable additives usable herein include, for example, surfactants and viscosity modifiers.
  • the adhesive composition of the present invention can be advantageously used, for example, in the form of an adhesive film.
  • the thickness of the adhesive film is not particularly limited, it is generally in the range of 5 to 1 ,000 ⁇ m.
  • the adhesive film may be produced by coating the adhesive composition precursor of the present invention on a suitable substrate and drying the coating. Coating means may be the same as that commonly used in the production of conventional adhesive films.
  • drying conditions are not particularly limited. In general, however, drying is carried out at a temperature of 60 to 100°C for several seconds to one hr from the viewpoint of preventing the solvent from remaining unremoved and, in addition, preventing excessive progress of the curing reaction of the composition at the time of drying.
  • Substrates on which the precursor may be coated include plastic films, such as polyimide and polyester films, metallic foils, such as copper and aluminum foils, and the like.
  • the product may be utilized as an adhesive sheet or an adhesive tape comprising a layer of an adhesive film and a substrate.
  • the adhesive film as such may be used.
  • the substrate may be a release film which, in use of the adhesive film, is entirely removed.
  • the thickness of the adhesive film and the composition of the adhesive composition are suitably prepared so that any of the components constituting the composition does not flow out from the end face of the film during the thermocompression bonding.
  • the formulation of the adhesive composition is determined so that the tensile storage modulus of the cured adhesive film was not less than 1010 dyne/cm ⁇ at 60°C.
  • This adhesive composition is best suited as an adhesive for an FPC protection film which has high dynamic folding resistance at 60°C and can be repeatedly folded.
  • the adhesive for an adhesive film for an FPC protection film is preferably such that the shrinkage of the adhesive film after the thermocompression bonding is not more than 0.1%.
  • the "shrinkage of the film” refers to the percentage of a reduction in the dimension of the adhesive film upon thermocompression bonding (after curing), relative to the dimension of film before thermocompression bonding (before curing).
  • a solubility test was carried out according to the following procedure in order to evaluate the solubility of a phenoxy resin in a mixed solvent composed of methyl ethyl ketone (MEK) and methanol (MeOH).
  • MEK methyl ethyl ketone
  • MeOH methanol
  • Fig. 1 a correlation diagram (a triangular diagram) showing the compatibility of a three-component system of YP50S + MEK + MEOH.
  • O represents "Sol” or “Op, " and • "Ps.”
  • the stoichiometric amount of the dicyandiamide (DICY) relative to 10 parts by weight of the brominated epoxy resin is 0.53 part by weight, and the maximum solubility of DICY in MEOH is 5% by weight. Therefore, at least 11 parts by weight of MEOH is necessary to dissolve DICY. That is, for preparing a homogeneous solution of YP50S + MEK + MEOH + YDB400 (10 pbw) + DICY in which a concentration of the solid content is at least 5% by weight, a weight ratio of MEOH to MEK, MeOH/MEK, should be of not less than 0.005.
  • the DICY content is generally determined based on the contents of the non-brominated epoxy resin, the brominated epoxy resin, and the phenoxy resin.
  • the DICY content is preferably determined so that it amounts about 0.5 to 1.5 times of the epoxy equivalent of the total epoxy resin.
  • the amounts of the components (a) to (c) (parts by weight) were as specified in Table 3, and the amount of the component (d) added was the stoichiometric amount determined by the following equation:
  • the composition of the resin solution was regulated so that the weight ratio of MEOH to MEK, MeOH/MEK, was in the range of 0.1 to 0.4 and the concentration of the resin component composed of the above components (a) to (d) was in the range of 10 to 50% by weight.
  • the thickness of the adhesive composition layer after drying was 30 ⁇ m.
  • the adhesive film prepared in each example was used before the thermosetting of the adhesive composition and subjected to a non-combustibility test according to the procedure set forth in UL94 to evaluate whether each adhesive film could satisfy the VO requirement.
  • the results of the evaluation are summarized in the following Table 3. In this test, the non-combustibility was evaluated as "passed” when the VO requirement was satisfied; and as “failed” when the VO requirement was not satisfied.
  • the adhesive films prepared in Examples 1 and 2 were used. A square cut having a size of about 35 mm x 35 mm was provided on the polyimide film in each of the adhesive films, and the length of one side of the square was accurately measured. Thereafter, a 25 ⁇ m-thick film of "KAPTON V (tradename, noted above)" was stacked on the bonding face of each of the adhesive films, followed by thermocompression bonding under conditions of a temperature of 180°C, a bonding time of 1 min, and a pressure of 10 kg/cm ⁇ . After one hour has passed from the completion of the thermocompression bonding at 180°C, the length of one side of the square was measured again and compared with the length of one side before the application to determine a percentage change ( ⁇ L).
  • KAPTON V tradename, noted above
  • the ⁇ L values for the adhesive films prepared in Examples 1 and 2 were respectively -0.02% and -0.03%. "-" in the ⁇ L value indicates that the dimension after the application was smaller than the dimension before the application. For both the adhesive films, the percentage change in dimension was not more than 0.1%, indicating that the dimensional stability was good.
  • Example 9 was used.
  • the adhesive film this obtained was evaluated for the dimensional stability in the same manner as described above. Since the adhesive film prepared in
  • Comparative Example 9 contained neither antimony pentaoxide and brominated epoxy resin, the ⁇ L value was -0.11%, indicating that the dimensional stability was poor.
  • Example 1 the adhesive films prepared in Example 1 and Comparative Example 9 were used.
  • the adhesive composition face and a 30 ⁇ m- thick rolled copper foil were stacked on top of the other.
  • Thermocompression bonding was first performed under conditions of a temperature of 180°C, a bonding time of one min, and a pressure of 20 kg/cm 2 and then under conditions of a bonding time of four hr, a
  • the bonded copper foil was peeled at a peel angle of 180° and a peel rate of 50 mrn/min to determine the peel strength as the adhesive strength.
  • the adhesive strength of the adhesive film prepared in Example 1 was 0.57 kg/cm
  • the adhesive strength of the adhesive film prepared in Comparative Example 9 was 0.45 kg/cm.
  • Examples 6 and 7 and Comparative Example 10 An adhesive film of Example 6 was prepared in the same manner as in Example 1 , except that a 50 ⁇ m-thick aluminum foil was used instead of the polyimide film. Further, adhesive films of Example 7 and Comparative Example 10 were prepared in the same manner as in Example 6, except that the same adhesive composition precursors as prepared in Example 2 and the same adhesive composition precursors as prepared in Comparative Example 9 were used respectively in Example 7 and Comparative Example 10.
  • Each of the adhesive films was put on a hot plate kept at 180°C so that the whole surface of the aluminum foil in each of the adhesive films came into contact with the surface of the hot plate. In this state, heating was performed for one min. Thereafter, the warpage (radius of curvature) of each of the adhesive films was measured, and the created stress was calculated based on the warpage.
  • the stress (kg/cm 2 ) was determined by the following equation (2):
  • E represents the modulus of elasticity
  • hi, h2 and ⁇ respectively represent the thickness of the adhesive layer
  • the stress determined by the above calculation for the adhesive films was 0.4 kg/cm 2 for Example 6, 0.5 kg/cm 2 for Example 7, and 1.4 kg/cm 2 for Comparative
  • Example 10 The lower this stress, the better dimensional stability.
  • the present invention can provide an adhesive which comprises a phenoxy resin, an epoxy resin, and a curing agent and possesses noncombustibility satisfying the VO requirement and, in addition, excellent performance (such as adhesive properties and dimensional stability) as an adhesive film for an FPC protection film.
  • an adhesive composition precursor is provided which can be advantageously used as a starting material for the preparation of the above adhesive composition.
  • Fig. 1 is a triangular diagram showing the compatibility of a three-component system of YP50S + MEK + MEOH.
  • Fig. 2 is a triangular diagram showing the compatibility of a four-component system of YP50S + MEK + MEOH + YDB400 (10 pbw).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

L'invention concerne une composition adhésive contenant une composante de résine comprenant une résine phénoxy, une résine époxyde et un dicyandiamide, possédant une non combustibilité satisfaisant la condition VO et, de plus, un excellent rendement (tel que des propriétés adhésives et une stabilité dimensionnelle) sous la forme d'une couche mince adhésive pour une couche mince de protection de circuit imprimé souple. La résine époxyde comprend une résine époxyde bromée et les particules colloïdales de pentaoxyde d'antimoine dans la gamme allant de 13 à 60 % en poids sur la base de la quantité totale de la composition adhésive.
EP99902053A 1998-02-05 1999-01-13 Composition adhesive et son precurseur Withdrawn EP1053280A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP10024414A JPH11217553A (ja) 1998-02-05 1998-02-05 接着剤組成物及びその前駆体
JP2441498 1998-02-05
PCT/US1999/000158 WO1999040150A1 (fr) 1998-02-05 1999-01-13 Composition adhesive et son precurseur

Publications (1)

Publication Number Publication Date
EP1053280A1 true EP1053280A1 (fr) 2000-11-22

Family

ID=12137509

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99902053A Withdrawn EP1053280A1 (fr) 1998-02-05 1999-01-13 Composition adhesive et son precurseur

Country Status (6)

Country Link
EP (1) EP1053280A1 (fr)
JP (1) JPH11217553A (fr)
KR (1) KR20010040644A (fr)
CN (1) CN1289352A (fr)
BR (1) BR9910827A (fr)
WO (1) WO1999040150A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003268337A (ja) * 2002-03-15 2003-09-25 Denki Kagaku Kogyo Kk 粘接着剤組成物及び粘接着シート
CN100432170C (zh) * 2003-05-20 2008-11-12 长兴化学工业股份有限公司 树脂组合物及含此组合物的背胶超薄铜箔介电层材料
JP5253315B2 (ja) * 2009-07-27 2013-07-31 大成プラス株式会社 溶剤型エポキシ接着剤及び接着方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4282136A (en) * 1979-04-09 1981-08-04 Hunt Earl R Flame retardant epoxy molding compound method and encapsulated device
JPS59136319A (ja) * 1983-01-25 1984-08-04 Nissan Chem Ind Ltd 難燃性基板エポキシ樹脂組成物
US4756954A (en) * 1986-01-22 1988-07-12 The Dow Chemical Company Epoxy resin laminating varnish and laminates prepared therefrom
JPH0692572B2 (ja) * 1988-11-28 1994-11-16 日立化成工業株式会社 銅張積層板用銅箔接着剤
JPH061961A (ja) * 1992-06-22 1994-01-11 Yokohama Rubber Co Ltd:The 接着剤組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9940150A1 *

Also Published As

Publication number Publication date
KR20010040644A (ko) 2001-05-15
CN1289352A (zh) 2001-03-28
BR9910827A (pt) 2001-03-20
WO1999040150A1 (fr) 1999-08-12
JPH11217553A (ja) 1999-08-10

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