EP1068277A1 - Composition adhesive et precurseur de cette composition - Google Patents

Composition adhesive et precurseur de cette composition

Info

Publication number
EP1068277A1
EP1068277A1 EP99909905A EP99909905A EP1068277A1 EP 1068277 A1 EP1068277 A1 EP 1068277A1 EP 99909905 A EP99909905 A EP 99909905A EP 99909905 A EP99909905 A EP 99909905A EP 1068277 A1 EP1068277 A1 EP 1068277A1
Authority
EP
European Patent Office
Prior art keywords
adhesive composition
resin
epoxy resin
weight
resin component
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Withdrawn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
EP99909905A
Other languages
German (de)
English (en)
Inventor
Yuji Hiroshige
Kohichiro Kawate
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 EP1068277A1 publication Critical patent/EP1068277A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • 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

Definitions

  • the present invention relates to an adhesive composition
  • an adhesive composition comprising, as a base, a resin component containing a phenoxy resin, an epoxy resin and a curing agent, and an adhesive composition precursor as a raw material of such a composition.
  • thermoplastic resins As a material of an adhesive film for FPC (flexible printed circuit board) protective film, various adhesive compositions obtained by combination of thermoplastic resins and epoxy resins as thermosetting resins have hitherto been known (see, for example, Japanese Unexamined Patent Publication (Kokai) Nos. 9-132710, 9-125037, 5-5085, 3-6280, 2- 145676, 62-274690, 60-130666, 1-135844 and 61-43550).
  • an adhesive film formed from a composition containing a phenoxy resin, an epoxy resin and a curing agent is comparatively superior in performances such as heat resistance, adhesion to metal parts, etc. and, therefore, the adhesive film has hitherto been considered to be useful. It is also disclosed to use a polyester resin or various elastomers in place of a phenoxy resin, as the thermoplastic resin. Furthermore, dicyanamide is often used, comparatively, because it is particularly superior in potentiality.
  • the above-described adhesive composition containing a phenoxy resin, an epoxy resin and dicyandiamide as a curing agent, as a main component has a drawback in that a dimensional change caused by a stress produced during the thermal curing process is comparatively large. Reduction in such a dimensional change, i.e. improvement of the dimensional stability, is further required in the usage of the adhesive for FPC protective film. In the above-described conventional composition, however, it was very difficult to respond to such a requirement.
  • an average particle diameter of the antimony pentaoxide powder is normally not less than 0 5 ⁇ m, sedimentation of the powder is liable to arise due to gravity and it was difficult to obtain a composition in the state where the respective components are uniformly dispersed That is, in case of forming an adhesive composition containing the antimony pentaoxide powder, sedimentation of the antimony pentaoxide powder is liable to arise in a mixed solution of an active amount of the antimony pentaoxide, a resin component and a solvent Therefore, it was difficult to realize the state (structure) where the respective components are uniformly mixed. Such a nonuniform structure causes deterioration of the adhesion, which results in drastic deterioration of the performance as the adhesive for FPC protective film
  • the object of the present invention is, therefore, to solve the above-described problems of the prior art and to provide an adhesive composition comprising a phenoxy resin, an epoxy resin and a curing agent, which is superior in performance as an adhesive for FPC protective film, particularly dimensional stability and adhesion. .
  • a further object of the present invention is to provide an adhesive composition precursor suited to provide such an adhesive composition
  • an adhesive composition comprising a resin component containing a phenoxy resin, an epoxy resin and a curing agent, characterized in that said resin component further contains a polyester polyol and further comprises an inorganic colloid dispersed in said resin component
  • an adhesive composition precursor capable of affording said adhesive composition after drying, characterized in that said precursor comprises: (i) said resin component, and (ii) an inorganic particle sol containing a dispersion medium and said inorganic colloid dispersed in said dispersion medium.
  • the adhesive composition of the present invention is a composition comprising, as a base, a resin component containing a phenoxy resin, an epoxy resin and a curing agent, characterized in that said resin component further contains a polyester polyol (hereinafter, sometimes, referred to as a "polyol") and an inorganic colloid in a predetermined ratio
  • a resin component containing a phenoxy resin, an epoxy resin and a curing agent
  • said resin component further contains a polyester polyol (hereinafter, sometimes, referred to as a "polyol”) and an inorganic colloid in a predetermined ratio
  • such a dimensional stability (represented by a dimensional change (%), a measuring method of which is described hereinafter) can be reduced to 0 1 % or less
  • a peel adhesive force (which means a " 180° peel adhesive force” hereinafter unless otherwise stated) can be increased to 700 g/cm or more
  • the operation of the above polyol to be contained in the resin component lies in improvement in interfacial adhesive force between the adhesive composition and adherend, first, because the polyol has two or more hydroxyl groups in the molecule.
  • a cured article of the adhesive composition contains a polyol
  • the flexibility of the cured article is improved and the peel adhesive force is increased.
  • the polyol can efficiently increase the crosslink density of the cured article without deteriorating the flexibility of the cured article, it also contributes to the improvement in dimensional stability.
  • the content of the above polyol is not specifically limited as far as the effect of the present invention is not adversely affected, but is normally within the range from 0 5 to 20% by weight based on the total amount of the adhesive composition.
  • the content of the polyol is less than 0.5% by weight, the peel adhesive force and dimensional stability are likely to be lowered.
  • the content exceeds 20% by weight, other performances of the adhesive composition (e.g nonflammability described hereinafter) are likely to be lowered From such a point of view, the preferable content of the polyol is within the range from 1 to 15% by weight based on the total amount of the adhesive composition.
  • polyol i.e. "polyester polyol” used herein means a compound which contains one or more ester bonds and two or more hydroxyl groups in the molecule and has a number-average molecular weight of 100 to 18,000, suitably 200 to 10,000, particularly suitably 300 to 6,000 The number-average molecular weight less than 100 causes a problem that, after heat treatment (thermal curing), an effectively increased dimensional stability may not be obtained, and the molecular weight above 18,000 may cause a reduction of the adhesive force
  • the polyol for example, caprolactonepolyol is suitable because of its good compatibility with other resin components such as phenoxy resin, epoxy resin, etc.
  • the kind and addition amount of the polyol are selected to impart high dynamic bending resistance to the cured article of the adhesive composition without reducing the elasticity at the temperature of not less than 60°C
  • the inorganic colloid used in combination with the polyol is normally contained in the dispersion in the form of colloidal particles, sedimentation of the colloidal particles does not arise due to gravity and the colloidal particles can be stably dispersed Accordingly, in the adhesive composition formed by drying such a dispersion of the present invention, the respective components can be uniformly dispersed, and peel adhesive force and dimensional stability of the composition can be efficiently improved
  • the content of inorganic colloid is not specifically limited as far as the effect of the present invention is not adversely affected, but is normally within the range from 1 to 50% by weight based on the total amount of the adhesive composition
  • the content of the inorganic colloid is less than 1% by weight, the dimensional stability is likely to be lowered
  • the peel adhesive force is likely to be lowered
  • the preferable content of the inorganic colloid is within the range from 2 to 45% by weight based on the total amount of the adhesive composition
  • the term "inorganic colloid” used herein normally means fine particles of the inorganic colloid having an average particle diameter within the range from 1 to 100 nm
  • An inorganic colloid for example those obtained by mixing an inorganic particle sol with a resin component to disperse the inorganic particle sol into the resin component, is suitable
  • the inorganic particle sol is a mixture of (i) a dispersion medium and (n) an inorganic particle sol.
  • the adhesive composition of the present invention is an adhesive composition, wherein the above epoxy resin contains a brominated epoxy resin and the above inorganic colloid is a colloid of antimony pentaoxide and, furthermore, the total proportion of the brominated epoxy resin and the colloid of antimony pentaoxide is within the range from 13 to 60% by weight based on the total amount of the adhesive composition
  • Such an adhesive composition can show the nonflammability of the level V0 or higher when the nonflammability is evaluated by the level of the nonflammability defined by the standard UL-94
  • the adhesive composition can have the nonflammability enough to satisfy the standard V0
  • the amount of the brominated epoxy resin and antimony pentaoxide particles used when the total proportion of them is less than 13% by weight based on the total amount of the adhesive composition, it is impossible to satisfy the above standard V0
  • the peel adhesive force is lowered
  • brominated epoxy resin used herein means an epoxy resin obtained by introducing a bromine atom into the molecule, for example, those having a structure wherein one or more hydrogen atoms of the benzene ring in the molecule of a bisphenol type epoxy resin are substituted with bromine atoms
  • the epoxy resin other than this "brominated epoxy resin” is referred to as a
  • non-brominated epoxy resin to define it by distinguishing from the brominated epoxy resin
  • resin component in the adhesive composition of the present invention means a mixture of a phenoxy resin, an epoxy resin, a curing agent, and a polyol
  • An optionally contained additional component, a solvent, and an inorganic colloid are not contained in the resin component
  • the optionally contained additional component include (i) a thermoplastic polymer such as an acrylic elastomer, etc , and additives such as (ii) a curing accelerator and (iii) a tackifier, a plasticizer, an antioxidant, a pigment, a dye, a filler other than an inorganic colloid, etc.
  • the content of the resin component, other than the polyol, contained in the adhesive composition is not also limited specifically as far as the effect of the present invention is not adversely affected.
  • the contents of the (a) phenoxy resin, (b) non-brominated epoxy resin, (c) brominated epoxy resin and (d) curing agent are as follows:
  • phenoxy resin 40 to 95% by weight, suitably 50 to 90% by weight
  • non-brominated epoxy resin 4 to 40% by weight, suitably 5 to 35% by weight
  • brominated epoxy resin 4 to 50% by weight, suitably 5 to 40% by weight, and
  • (d) curing agent 0.1 to 7% by weight, suitably 0.5 to 5% by weight, based on the total amount of the resin component.
  • curing agent means a compound capable of reacting with at least epoxy resin in the curing reaction or crosslinking reaction, such as dicyandiamide or a derivative thereof. Dicyandiamides and derivatives thereof are superior in potentiality and can efficiently enhance the storage stability of the composition and precursor.
  • An adhesive composition of the present invention and a precursor thereof, and an adhesive film derived from the adhesive composition precursor of the present invention will be described in more detail hereinafter.
  • Adhesive Composition The resin component contained in the adhesive composition of the present invention is normally composed of the following components: (a) a phenoxy resin,
  • the phenoxy resin is one of the components that contributes to the improvement of the adhesive force of the adhesive composition
  • an intermolecular attraction force between hydroxyl groups of a polymer molecule constituting the phenoxy resin and the adhered surface and pliability (flexibility) of the resin itself contribute to the improvement of the peel adhesive force
  • the kind and addition amount of the phenoxy resin are selected so that the glass transition temperature of the cured composition does not become 70°C or less Consequently, the dynamic bending resistance of the cured composition is enhanced, thereby making it possible to effectively prevent breakage or peeling of the adhesive layer in use
  • the non-brominated epoxy resin operates by increasing the glass transition temperature of the cured composition by reaction with the curing agent, such as dicyandiamide A relatively high glass transition temperature is advantageous for enhancing heat resistance of the composition It is preferred that the kind and addition amount of the non-brominated resin are selected so that the glass transition temperature of the cured composition does not become 70°C or less As the non-brominated epoxy resin
  • the brominated epoxy resin enhances nonflammability of the composition, as described above It also operates by enhancing solubility of the phenoxy resin in a specific solvent (e g mixed solvent containing methyl ethyl ketone and methanol, etc ) A mixed solvent of methyl ethyl ketone and methanol has a comparatively large evaporation rate Accordingly, it is preferable to use brominated epoxy resin and phenoxy resin in combination so as to reduce the amount of the residual solvent in the adhesive composition after drying (e g adhesive film, etc ) and to realize a uniform structure of the respective components
  • brominated epoxy resin also has the same operation as that of the non-brominated epoxy resin with respect to its reaction with the curing agent It is suitable that the kind and addition amount of the brominated resin are selected so that a good balance between nonflammability of the composition, solubility of the phenoxy resin, and glass transition temperature (exceeding 70°C) of the composition after curing can be obtained As the bromin
  • the resin component can contain the other additional component, in addition to the above components (a) to (e) It is preferred that the amount of such an additional component is selected in the same manner as that in case of the above other resin component
  • the adhesive composition precursor is a raw material of an adhesive composition, capable of affording an adhesive composition of the present invention after drying
  • This precursor is normally composed of the above resin component, particles of an inorganic colloid (e g a colloid of antimony pentaoxide, etc ) and a solvent
  • the inorganic colloid is normally mixed with the above other component in the form of a sol, and then uniformly dispersed in a vehicle of the above l esin component and solvent A sol, such as those obtained by dispersing colloidal particles in an organic solvent, is normally used It is preferred that the solvent used in the sol is selected taking the solubility in the above resin component therein into consideration Among solvents, methyl ethyl ketone is preferred because its solubility in the above resin component is typically good and dispersion stability of the sol in the precursor (particles) is not likely to be deteriorated
  • the concentration of the inorganic colloid in the precursor composition is normally within the range from 1 to 50% by weight
  • the adhesive composition precursor can be prepared according to various procedures One preferred preparation method will be described by way of the example of using a colloid of antimony pentaoxide as the inorganic colloid
  • the resin component is mixed with a solvent to prepare a uniform resin solution
  • a suitable mixing means include using a high-speed mixer, a planetary mixer, a homomixer, a sand mill, etc.
  • the concentration of the resin solution is normally within the range from 5 to 70% by weight
  • an antimony pentaoxide sol is added to prepare a uniform dispersion using a mixing means, thereby obtaining an adhesive composition precursor composed of the dispersion
  • a precursor containing antimony pentaoxide particles dispersed in the above resin component, uniformly and stably
  • the same mixing means as described above can also be used
  • a mixed solvent containing methyl ethyl ketone is suitable as described above. In this case, the weight ratio (MeOH/MEK) of methyl ethyl ketone
  • the mixed solvent may contain solvents other than methyl ethyl ketone and methanol.
  • alcohols such as ethanol, isopropyl alcohol, n-propyl alcohol, n- butyl alcohol, sec-butyl alcohol, t-butyl alcohol, etc and nitrogen-containing solvents such as acetonitrile, etc.
  • ethanol has good solubility in dicyandiamide and its evaporation rate is lower than that of methyl ethyl ketone
  • its use does not reduce the evaporation rate of the mixed solvent drastically Therefore, uniformity of the coated film can be effectively improved without decreasing the drying rate of the coated film
  • the adhesive composition precursor can contain various additives as far as the effect of the present invention is not adversely affected
  • suitable additives include surfactants, viscosity adjustors, etc Adhesive Film
  • the adhesive composition of the present invention can be used, for example, in the form of an adhesive film
  • the thickness of the adhesive film is not specifically limited, but is normally within the range from 5 ⁇ m to 1 ,000 ⁇ m
  • the adhesive film can be produced by coating the adhesive composition precursor of the present invention on a substrate, followed by drying
  • a coating means the same means as that in case of a normal adhesive film can be used
  • suitable coating means include, for example, those using a knife coater, bar coater, die coater, etc
  • the drying conditions are not specifically limited, but are preferably a heating temperature of 50°C to 120°C with a heating time of several minutes to one hour so that residual solvent does not remain and curing of the composition does not proceed during the drying
  • the substrate there can be used plastic films, such as polyimide films, polyester films, etc.; and metal foils, such as copper foils, aluminum foils, etc
  • plastic films such as polyimide films, polyester films, etc.
  • metal foils such as copper foils, aluminum foils, etc
  • an adhesive sheet ribbon
  • the adhesive film alone can be used after removing the release for use.
  • the bonding can-be completed by using a heat bonding operation including heating at 100°C to 180°C for 1 to 2 minutes and pressurizing at 2 to 50 kg/cm ⁇ . After bonding, the heating operation can be subsequently performed at 150°C to 170°C for 1 to 5 hours It is preferred that thickness of the adhesive film or composition of the adhesive composition is appropriately adjusted so that the composition component hardly flows out from the film end surface during the heat bonding operation
  • the formulation of the adhesive composition is adjusted so that the tensile storage modulus at 60°C of the cured adhesive film is 1 X 10 ⁇ dyne/cm ⁇
  • shrinkage factor of a film means a percentage of a ratio of the reduction in size after heat bonding (after curing) to the size before heat bonding (before curing)
  • a phenoxy resin (trade name YP50S, having a number-average molecular weight of 1 180, a weight-average molecular weight of 58,600, and manufactured by Tohto Chemical Co , Ltd ), 20 0 g of a polyester polyol-containing phenoxy resin (trade name PKHM-30, containing about 30% by weight of a polyester polyol, and manufactured by Union Carbide Co ), 10 0 g of a bisphenol A type epoxy resin (trade name DER332, epoxy equivalent 173, and manufactured by Dow Co ), 10 0 g of a brominated epoxy resin (trade name YDB400, epoxy equivalent 400, and manufactured by Tohto Chemical Co , Ltd ), and 1 74 g of dicyandiamide (Dicy) (trade name Amicure CGI 200, having an amine equivalent of 21, and manufactured by ACR Co ) were dissolved in a mixed solvent of 225 g of methyl ethyl ketone and 43 5
  • a rectangular surface of about 70 mm x 35 mm was drawn on the polyimide side of an adhesive film laminated with a polyimide film by using a cutter knife. The length of each side was measured. Then, a KAPTON V film, having a thickness of 25 ⁇ m, was layered on the adhesive surface of the adhesive film, heat-bonded at 180°C under a pressure of 10 kg/cm ⁇ for 1 minute, and then allowed to stand at room temperature for 1 hour. Subsequently, the adhesive film after heat bonding was heat-treated at 150°C for 4 hours and further allowed to stand at room temperature for 1 hour.
  • evaluation of the dimensional stability was performed with respect to the dimensional change (%) and timing of the evaluation was as follows: First time: the evaluation was performed after heat bonding at 120°C for 1 minute and following standing at room temperature (see data of the item ® in Table 2), and Second time: the evaluation was performed after heat bonding at 180°C for 1 minute and following standing at room temperature, a heat treatment at 150°C for 4 hours and standing at room temperature (see data of the item ® in Table 2). The evaluation results described in Table 2 were obtained.
  • a rolled copper foil having a thickness of 30 ⁇ m was layered on the adhesive surface of the adhesive film laminated with a polyimide film, heat-bonded at 180°C under a pressure of 20 kg/cm ⁇ for 1 minute, and then heat-treated at 150°C for 4 hours
  • the copper foil layered on the adhesive film was peeled off at a peel angle of 180° and a peel rate of 50 mm/minute
  • An integrated average value of the resulting values was taken as a measure of the adhesive force (peel adhesive force, g/cm)
  • the evaluation results described in Table 2 were obtained D Measurement of Viscoelasticity
  • a dispersion of the adhesive composition precursor prepared in the above step (1 ) was coated on a PET film subjected to a peeling treatment and then dried The adhesive film was peeled from the PET film and the single adhesive film was sandwiched between release papers The resulting laminate was heat-bonded at 180°C under a pressure of 20 kg/cm ⁇ for 1 minute
  • Tg Glass Transition Temperature
  • an adhesive composition precursor and an adhesive film (adhesive composition) of each example were prepared
  • the content of dicyandiamide (Dicy) was adjusted so that the epoxy equivalent of the total epoxy resins was the same as the active hydrogen equivalent of Dicy
  • the resin component PKMH-301 described in Table 1 is a polyester polyol-containing phenoxy resin (containing about 30%) by weight of a polyester polyol, manufactured by Union Carbide Co , Ltd and sold under the trade designation PKMH-301).
  • an adhesive composition precursor and an adhesive film of this example were prepared According to the same manner as that described in Example 1, the characteristics of the adhesive film were evaluated and are described in Table 2.
  • an adhesive composition precursor and an adhesive film of this example were prepared According to the same manner as that described in Example 1, the characteristics of the adhesive film were evaluated and are described in Table 2.
  • Example Example Example 4 Comp Comp 1 2 3
  • Example Example 5 Comp Comp 1 2 3
  • Adhesive force 780 776 819 818 570 (g/cm)
  • First time Films were heat-bonded at 120°C under a pressure of 10 kg/cm - for 2 minutes and then allowed to stand at room temperature for 1 hour (see data of item ⁇ in the table)
  • Second time Films were heat-bonded at 120°C under a pressure of 10 kg/cm ⁇ for 2 minutes and then allowed to stand at room temperature for 1 hour Subsequently, the resulting adhesive film was heat-treated at 170°C for 2 minutes and then allowed to stand at room temperature for 1 hour (see data of item ⁇ in the table)
  • Example 6 a polyester polyol resin (trade name PLACCEL 210, number-average molecular weight 1,000, manufactured by Daiseru Chemical Industries Co , Ltd ),
  • Example 7 a polyester polyol resin (trade name PLACCEL 240, number-average molecular weight 4,000, manufactured by Daiseru Chemical Industries Co , Ltd ), and
  • Example 8 a polyester polyol resin (trade name PLACCEL TP249, number- average molecular weight. 16,000, manufactured by Daiseru Chemical Industries Co., Ltd.).
  • the dimensional stability and adhesion can be simultaneously improved, particularly, in an adhesive composition comprising a resin component containing a phenoxy resin, an epoxy resin and a curing agent. Accordingly, the resulting adhesive composition can be advantageously utilized as an adhesive or FPC protective film According to the present invention, there can also be provided a precursor capable of deriving such an adhesive composition

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une composition adhésive utile comme adhésif pour une pellicule protectrice de plaquette de circuit imprimé souple. Cette composition présente une stabilité de dimension et d'adhésion particulièrement importante. Elle comprend un composant résine contenant une résine phénoxy, une résine époxy et un agent de durcissement. Elle est caractérisé par la présence additionnelle d'un polyester polyol et d'un colloïde inorganique dispersés dans le composant résine.
EP99909905A 1998-03-31 1999-03-08 Composition adhesive et precurseur de cette composition Withdrawn EP1068277A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP8663198 1998-03-31
JP10086631A JPH11293217A (ja) 1998-03-31 1998-03-31 接着剤組成物およびその前駆体
PCT/US1999/005017 WO1999050369A1 (fr) 1998-03-31 1999-03-08 Composition adhesive et precurseur de cette composition

Publications (1)

Publication Number Publication Date
EP1068277A1 true EP1068277A1 (fr) 2001-01-17

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP99909905A Withdrawn EP1068277A1 (fr) 1998-03-31 1999-03-08 Composition adhesive et precurseur de cette composition

Country Status (4)

Country Link
EP (1) EP1068277A1 (fr)
JP (1) JPH11293217A (fr)
AU (1) AU2900099A (fr)
WO (1) WO1999050369A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002064276A (ja) * 2000-08-22 2002-02-28 Nippon Steel Chem Co Ltd 光又は熱硬化性樹脂組成物及び多層プリント配線基板
JP4605681B2 (ja) * 2000-11-28 2011-01-05 日本化薬株式会社 ポリクレゾール樹脂、エポキシ樹脂組成物及びその硬化物
JP2002327165A (ja) * 2001-04-20 2002-11-15 Three M Innovative Properties Co 熱硬化性の接着剤フィルム及びそれを用いた接着構造
DE102005027551A1 (de) 2005-06-14 2006-12-21 Basf Ag Verfahren zur Herstellung eines Verbundstoffes aus Steinen und einem Kunststoff
US10626308B2 (en) * 2015-09-15 2020-04-21 3M Innovative Properties Company Adhesive composition and an article manufactured therefrom

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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
JPH021789A (ja) * 1988-02-24 1990-01-08 Matsushita Electric Works Ltd 電気回路板
US5073605A (en) * 1988-07-14 1991-12-17 General Electric Company Bromine-bisphenol reacted bisphenol and novolak epoxy resins with polyphenylene ether
JP2915168B2 (ja) * 1991-05-29 1999-07-05 ポリプラスチックス株式会社 難燃性ポリブチレンテレフタレート樹脂組成物
CA2189325A1 (fr) * 1995-03-10 1996-09-19 Youichi Ohara Compositions de resine ignifuge de terephtalate de polyethylene

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Title
See references of WO9950369A1 *

Also Published As

Publication number Publication date
AU2900099A (en) 1999-10-18
JPH11293217A (ja) 1999-10-26
WO1999050369A1 (fr) 1999-10-07

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