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
  • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/10—Adhesives in the form of films or foils without carriers
• • 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
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
• • 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
  • C09J2453/00—Presence of block copolymer
• • 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
  • C09J2463/00—Presence of epoxy resin
• • 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
  • C09J2471/00—Presence of polyether

Definitions

• the present invention relates to a resin composition. More specifically, the present invention relates to a resin composition suitable for an adhesive film for electric / electronic use or a coverlay film for a printed wiring board. Moreover, this invention relates to the adhesive film produced using this resin composition, and a coverlay film.
• the adhesive film materials used in the above applications are inherently flammable, so that they can be used as industrial materials in addition to satisfying general chemical and physical properties in a well-balanced manner. That is, there are many cases where flame retardancy is required. In many cases, particularly when used in home appliances, a high level of flame retardancy such as “flame retardancy based on UL94 satisfies V-0 or VTM-0” is required.
• a method for imparting flame retardancy to a resin material such as an adhesive film
• a method of adding a halogen-based organic compound as a flame retardant and further adding an antimony compound as a flame retardant aid to the resin can be mentioned.
• a phosphorous flame retardant formulation for example, a phosphorous flame retardant formulation is employed.
• phosphate esters such as trimethyl phosphate, triphenyl phosphate, tricresyl phosphate and the like can be used as a flame retardant, The range of the flame retardant content when the flame retardant is contained in the coverlay film described in the document is shown.
• the cover lay film described in Patent Document 1 is intended for application to a flexible printed wiring board, and has the above-described high flame retardancy, that is, “flame retardancy based on UL94 is V-0 or VTM-0. It is not described that "satisfying" is required. Therefore, the flame retardant content described in paragraph [0040] of Patent Document 1 achieves a high level of flame retardancy such as “flameability based on UL94 satisfies V-0 or VTM-0”. It is not intended. In order to achieve high flame retardancy such as “flame retardancy based on UL94 satisfies V-0 or VTM-0”, it is necessary to increase the content of the flame retardant.
• the frequency is 1 to 10 GHz. It has been clarified that the dielectric constant ( ⁇ ) and dielectric loss tangent (tan ⁇ ) in the high frequency region are increased, and electric signal loss in the high frequency region becomes a problem.
• the present invention can achieve low dielectric constant and low dielectric loss in a high frequency region, specifically, a frequency range of 1 to 5 GHz, and UL94 It is an object of the present invention to provide an adhesive film and a coverlay film for electric / electronic applications that can satisfy V-0 or VTM-0, and a resin composition used for producing them.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group.
• — (O—X—O) — is represented by the following structural formula (2).
• R 8 , R 9 , R 10 , R 14 , and R 15 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
• R 11, R 12, R 13 are the same or different, it is a hydrogen atom, a halogen atom or more than 6 alkyl group or a phenyl group having a carbon.
• -(YO)- is one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) arranged at random.
• R 16 and R 17 may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
• R 18 and R 19 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
• Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom.
• a and b each represents an integer of 0 to 300, at least one of which is not 0.
• c and d represent an integer of 0 or 1.
• thermoplastic elastomer (B) a thermoplastic elastomer, (C) a thermosetting resin other than the vinyl compound represented by the general formula (1), (D) a curing agent, and (E) containing an organic aluminum phosphinate, 10 to 50 parts by mass of the component (E) with respect to 100 parts by mass in total of the component (A), the component (B), the component (C), the component (D), and the component (E)
• the resin composition characterized by containing is provided.
• — (O—X—O) — of the component (A) is represented by the following structural formula (4)
• — (YO) — of the component (A) is Structural formula (5), or a structure represented by the following structural formula (6), or a structure represented by the following structural formula (5) and a structure represented by the following structural formula (6) are randomly arranged. It is preferable.
• — (YO) — of the component (A) has a structure represented by the structural formula (6).
• the thermoplastic elastomer of component (B) is a styrene-butadiene block copolymer, a styrene-ethylene / butylene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, or a polybutadiene. And at least one selected from the group consisting of styrene- (ethylene-ethylene / propylene) -styrene block copolymers.
• thermosetting resin of the component (C) is a biphenyl type epoxy resin, a naphthalene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, a bismaleimide, And at least one selected from the group consisting of carbodiimide and the like.
• the content of the thermoplastic elastomer of the component (B) includes the component (A), the component (B), the component (C), the component (D), and the component.
• the amount is preferably 10 to 60 parts by mass with respect to 100 parts by mass in total of (E).
• the content of the thermosetting resin of the component (C) is such that the component (A), the component (B), the component (C), the component (D), and the The amount is preferably 0.5 to 40 parts by mass with respect to 100 parts by mass in total of the component (E).
• the resin composition of the present invention may further contain (F) a filler.
• the component (A), the component (B), the component (C), the component (D), the component (E), and the component (F) with respect to a total of 100 parts by mass. 10 to 60 parts by mass of (F) is contained.
• the resin composition of the present invention may further contain (G) an organic peroxide.
• the resin composition of the present invention has a dielectric constant ( ⁇ ) of 3.0 or less and a dielectric loss tangent (tan ⁇ ) of 0.006 or less in the frequency range of 1 to 10 GHz of the cured product of the resin composition. preferable.
• the resin composition of the present invention preferably has flame retardancy based on UL94 satisfying V-0 or VTM-0.
• the present invention also provides an adhesive film produced using the resin composition of the present invention.
• the present invention also provides a coverlay film produced using the resin composition of the present invention.
• the present invention also provides a varnish containing the resin composition of the present invention.
• the adhesive film and coverlay film of the present invention have excellent electrical characteristics in a high frequency region after heating and curing, specifically, a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a frequency range of 1 to 10 GHz. ), It is possible to achieve low dielectric constant and low dielectric loss in a high frequency region, and flame retardancy based on UL94 satisfies V-0 or VTM-0. Moreover, the adhesive film and coverlay film of this invention show the adhesive strength outstanding with respect to the organic material or inorganic material used for printed wiring boards, such as a polyimide, a liquid crystal polymer, and a ceramic, after heat-hardening.
• the adhesive film and coverlay film of this invention are excellent in flexibility after heat-curing, they are suitable as an adhesive film and coverlay film for flexible printed wiring boards.
• the film of this invention is excellent in flexibility before heat-hardening, the workability
• the adhesive film and coverlay film of the present invention can be prepared using the resin composition of the present invention.
• a varnish containing the resin composition of the present invention may be applied to the film forming surface and then dried to form a film.
• the resin composition of the present invention contains the following components (A) to (E) as essential components.
• Component (A) Vinyl compound represented by the following general formula (1) and having a mass average molecular weight (Mw) of 500 to 4000
• R 1, R 2, R 3, R 4, R 5, R 6, R 7 are the same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, or It is a phenyl group.
• R 1, R 2, R 3, R 4, R 5, is preferably R 6, R 7 is a hydrogen atom.
• — (O—X—O) — is represented by the following structural formula (2).
• R 8 , R 9 , R 10 , R 14 , and R 15 may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
• R 8 , R 9 , R 10 , R 14 , and R 15 are preferably alkyl groups having 6 or less carbon atoms.
• R 11 , R 12 and R 13 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
• R 11 , R 12 and R 13 are preferably a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms.
• -(YO)- is a random arrangement of one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) It is a thing.
• — (YO) — is preferably an arrangement of one type of structure defined by the following structural formula (3).
• R 16 and R 17 may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
• R 16 and R 17 are preferably alkyl groups having 6 or less carbon atoms.
• R 18 and R 19 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
• R 18 and R 19 are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms.
• Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. Among these, it is preferable that Z is a methylene group.
• a and b each represents an integer of 0 to 300, at least one of which is not 0.
• c and d represent an integer of 0 or 1. Among these, c and d are preferably 1.
• R 8, R 9, R 10, R 14, R 15 is alkyl group having 3 or less carbon atoms
• R 11, R 12, R 13 is a hydrogen atom or alkyl group having 3 or less carbon atoms
• R 16 and R 17 are alkyl groups having 3 or less carbon atoms
• R 18 and R 19 are hydrogen atoms.
• — (O—X—O) — in the general formula (1) is preferably represented by the following structural formula (4).
• — (Y—O) — represents the structure represented by the following structural formula (5), the following structural formula (6), the structure represented by the following structural formula (5), and It is preferable to have a structure in which the structure represented by the following structural formula (6) is randomly arranged.
• -(YO)- preferably has a structure in which structures defined by the following structural formula (6) are arranged.
• the component (A) is the thermosetting property, heat resistance, and excellent electrical properties at high frequencies of the adhesive film and coverlay film prepared using the resin composition, that is, the frequency. This contributes to a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in the region of 1 to 10 GHz.
• component (A) acts as a compatibilizer for components (B) to (E) described below.
• the component (A) among the vinyl compounds represented by the general formula (1), those having a mass average molecular weight (Mw) of 500 to 4000 are used as follows.
• Mw mass average molecular weight
• the mass average molecular weight (Mw) is less than 500, the flexibility of the adhesive film and coverlay film prepared using the resin composition is lost, and the film becomes brittle and easily broken.
• the melt viscosity is too low during thermocompression bonding or heat curing, the film thickness uniformity may be impaired.
• the mass average molecular weight (Mw) exceeds 4000, the solubility is lowered, which causes a problem when preparing the resin composition.
• the component (A) among the vinyl compounds represented by the general formula (1), those having a mass average molecular weight (Mw) of 800 to 3500 are preferably used, and those having 1000 to 3000 are more preferably used.
• the method for producing the vinyl compound represented by the general formula (1) is not particularly limited, and may be produced by any method.
• chloromethylstyrene is added to a compound represented by the following general formula (7) in the presence of an alkali catalyst such as sodium hydroxide, potassium carbonate, sodium ethoxide, and the like, if necessary, benzyltri n-butylammonium bromide, 18- It can be obtained by reacting with a phase transfer catalyst such as crown-6-ether.
• an alkali catalyst such as sodium hydroxide, potassium carbonate, sodium ethoxide, and the like
• benzyltri n-butylammonium bromide 18- It can be obtained by reacting with a phase transfer catalyst such as crown-6-ether.
• — (O—X—O) and — (Y—O) — are as described above for formula (1).
• component (B) is an excellent electrical property (frequency 1 to frequency) of an adhesive film and a coverlay film prepared using the resin composition. This contributes to low dielectric constant ( ⁇ ) and low dielectric loss tangent (tan ⁇ ), film properties, and heat resistance in the 10 GHz region.
• styrene-butadiene block copolymer As the elastomer of component (B), styrene-butadiene block copolymer, styrene-ethylene / butylene-styrene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene, and , At least one selected from the group consisting of styrene- (ethylene-ethylene / propylene) -styrene block copolymers can be used. Among these, only any 1 type may be used and 2 or more types may be used. Which of these is used can be appropriately selected depending on the properties to be imparted to the adhesive film and the coverlay film produced using the resin composition.
• a styrene-ethylene / butylene-styrene block copolymer has high heat resistance due to high crystallinity of the portion of -ethylene / butylene-, and is used as an adhesive film and a coverlay film formed using the resin composition. It is preferable for imparting heat resistance.
• the styrene- (ethylene-ethylene / propylene) -styrene block copolymer has a crystallinity of the-(ethylene-ethylene / propylene)-moiety corresponding to that of the styrene-ethylene / butylene-styrene block copolymer.
• the adhesive strength to the substrate is higher than that of the styrene-ethylene / butylene-styrene block copolymer.
• the styrene-butadiene block copolymer has a low elastic modulus of an adhesive film and a coverlay film prepared using the resin composition, and unevenness present on the adherend surface during thermocompression bonding of the film. Therefore, the adhesive strength of the film is increased. Moreover, the flexibility after curing of the film is also excellent.
• the content of the component (B) is preferably 10 to 60 parts by mass with respect to 100 parts by mass in total of the components (A) to (E).
• the content of the component (B) is less than 10 parts by mass, the film properties of the adhesive film and coverlay film prepared using the resin composition, specifically, the folding resistance of the film alone is inferior.
• the amount of seepage during thermocompression increases, and the film thickness tends to be uneven.
• the content of the component (B) exceeds 60 parts by mass, the content of other components of the resin composition, in particular, the component (A) is reduced, so that the resin composition is used. The heat resistance of the adhesive film and the coverlay film is lowered.
• the content of the component (B) is more preferably 12 to 55 parts by mass, and 13 to 45 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). More preferably, it is a part.
• Component (C) Thermosetting resin other than the vinyl compound represented by the general formula (1)
• the component (C) is an adhesive film and a coverlay prepared using the resin composition. Contributes to the thermosetting and adhesive properties of the film.
• thermosetting resin used as the component (C) is not particularly limited as long as it is a thermosetting resin other than the vinyl compound represented by the general formula (1) as the component (A).
• the thermosetting resin used as the component (C) includes biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, bismaleimide, and carbodiimide. At least one selected from the group can be used.
• any 1 type may be used and 2 or more types may be used together. Which of these is used can be appropriately selected depending on the properties to be imparted to the adhesive film and the coverlay film produced using the resin composition.
• Epoxy resins such as biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolak type epoxy resin are excellent in compatibility with other components of the resin composition, and the resin composition An adhesive film and a cover lay film produced using a product are excellent in moisture resistance reliability.
• a biphenyl type epoxy resin is more preferable because the dielectric property of the resin itself is relatively good.
• bismaleimide when bismaleimide is used, the linear expansion coefficient after hardening of the adhesive film and coverlay film which are created using this resin composition becomes low.
• the content of the thermosetting resin of component (C) is 0.5 to 40 parts by mass with respect to 100 parts by mass in total of components (A) to (E). preferable.
• content of a component (C) is less than 0.5 mass part, there exists a problem that the adhesiveness of the adhesive film and coverlay film which are created using this resin composition becomes inadequate.
• the content of the component (C) is more than 40 parts by mass, the amount of oozing during thermocompression bonding of the adhesive film and coverlay film prepared using the resin composition becomes excessively large.
• the ratio of the component (C) in all the components increases, the properties of the component (C) inferior in heat resistance affect the entire adhesive film and coverlay film formed using the resin composition. .
• the content of component (C) is more preferably 1.0 to 30 parts by mass with respect to 100 parts by mass in total of components (A) to (E). More preferably, it is 5 to 15 parts by mass.
• the number average molecular weight ( Mn) is preferably from 150 to 2500 for reasons of thermosetting, adhesiveness, and post-curing mechanical properties of the adhesive film and coverlay film prepared using the resin composition.
• the thermosetting resin used as the component (C) is bismaleimide
• the number average molecular weight (Mn) is 150 to 3500. The heat of the adhesive film and coverlay film prepared using the resin composition It is preferable for reasons of curability, adhesiveness, and mechanical properties after curing.
• Component (D) Curing Agent
• the resin composition of the present invention contains an effective amount of a curing agent as the component (D).
• the curing agent used as component (D) is not particularly limited.
• phenol-based curing agent examples include monomers, oligomers, and polymers in general having a phenolic hydroxyl group. Examples thereof include triphenol methane resin and dicyclopentadiene type phenol resin.
• amine curing agent examples include triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4, 0] tertiary amine compounds such as undecene-7 (DBU), triethylenediamine, benzyldimethylamine, triethanolamine and the like.
• triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine
• DBU undecene-7
• 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine is preferred.
• imidazole curing agents examples include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl.
• imidazole compounds such as -4-imidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Of these, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-imidazole are preferable.
• acid anhydride-based curing agent examples include phthalic anhydride, maleic anhydride, dodecenyl succinic anhydride, trimellitic anhydride, benzophenone tetracarbanoic dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride. .
• any 1 type may be used among said hardening
• an imidazole-based curing agent is preferable because it exhibits an effect even if the addition amount is small.
• 2-phenyl-4,5 dihydroxymethylimidazole is a varnish obtained by diluting a resin composition with a solvent. It is preferable because the pot life and the shelf life of the adhesive film and coverlay film produced using the resin composition are improved.
• the effective amount of the curing agent varies depending on the type of the curing agent.
• the effective amount for each type of curing agent is shown below.
• the effective amount is more preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass in total of components (A) to (E). Further preferred.
• the effective amount is more preferably 1 to 10 parts by mass, and more preferably 1 to 3 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). Further preferred.
• the effective amount is more preferably 0.1 to 5 parts by mass, and 0.2 to 3 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). More preferably.
• the effective amount is more preferably 1 to 10 parts by mass with respect to 100 parts by mass in total of components (A) to (E), preferably 1 to 5 parts by mass. More preferably it is.
• Component (E) Aluminum organophosphinate
• component (E) contributes to the flame retardancy of an adhesive film and a coverlay film prepared using the resin composition.
• the organic aluminum phosphinate used as the component (E) is represented by the following general formula.
• R 1 and R 2 may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or a naphthyl group.
• the alkyl group may be linear, branched or cyclic. An alkyl group having 1 to 3 carbon atoms is preferable, and an ethyl group is more preferable.
• the organic aluminum phosphinate used as component (E) is preferably aluminum dialkylphosphinate, more preferably aluminum diethylphosphinate.
• the resin composition of the present invention uses an organoaluminum phosphinate as the component (E), so that an adhesive film and a coverlay film prepared using the resin composition have a flame retardancy based on UL94 of V-0. Or, VTM-0 is satisfied. It is also described in JP-A-2009-179774 and JP-A-2011-225883 that, when an organic phosphinate aluminum is used as a flame retardant, flame retardancy based on UL94 satisfies V-0 or VTM-0. Has been. However, in the former case, the electric signal loss in the high frequency region is not regarded as a problem, and the electrical characteristics in the high frequency region have not been studied at all.
• the relative dielectric constant at a frequency of 1 GHz or higher includes a resin having a relative dielectric constant of 2.9 or lower
• the relative dielectric constant of the resin composition at a frequency of 1 GHz or higher can be 3.0 or lower. Since the mass average molecular weight (Mw) of the resin having a relative dielectric constant of 2.9 or less at a frequency of 1 GHz or higher is as high as 1,000 to 300,000, it was used as a resin composition for adhesive films and coverlay films. In this case, the solubility is lowered, which causes a problem when preparing the resin composition.
• Mw mass average molecular weight
• the resin composition of the present invention contains 10 to 50 parts by mass of the component (E) with respect to 100 parts by mass in total of the components (A) to (E).
• the content of the component (E) is less than 10 parts by mass, the flame retardancy of the adhesive film and coverlay film prepared using the resin composition is lowered, and the flame retardancy based on UL94 is V-0 or Not satisfied with VTM-0.
• the component (E) exceeds 50 parts by mass, it becomes impossible to form a film when an adhesive film and a coverlay film are produced using the resin composition.
• the component (E) is preferably contained in an amount of 15 to 48 parts by mass, more preferably 18 to 45 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). More preferred.
• the resin composition of the present invention may contain the following components (F) and (G) as necessary in addition to the components (A) to (E).
• Component (F) Filler
• the resin composition of the present invention may contain a filler as the component (F) in addition to the components (A) to (E).
• a filler as the component (F)
• the adhesive film and coverlay film prepared using the resin composition of the present invention can have desired rheological properties, electrical properties, or physical properties, or Both can be granted.
• the filler used as the component (F) is appropriately selected according to the use of the adhesive film and the coverlay film prepared using the resin composition of the present invention. For example, a thermally conductive substance, an unnecessary radiation absorbing substance And ceramic dielectric materials.
• thermally conductive substance examples include oxides such as aluminum oxide and silicon dioxide, and nitrides such as aluminum nitride and boron nitride.
• unnecessary radiation absorbing material examples include iron oxides such as ferrite.
• ceramic dielectric material examples include barium titanate and titanium oxide.
• the content of the resin composition of the present invention is an amount necessary for exhibiting desired characteristics and an amount capable of forming a film.
• it is 10 with respect to a total of 100 mass parts of a component (A), a component (B), a component (C), a component (D), a component (E), and a component (F).
• It is preferably from 60 parts by mass from the viewpoint of dispersibility in the resin composition and processability of an adhesive film and a coverlay film prepared using the resin composition, and more preferably from 20 to 55 parts by mass. More preferably, it is 25 to 50 parts by mass.
• the shape is not particularly limited, and may be, for example, granular, powdery, flake shaped, etc.
• the maximum diameter) is preferably 0.5 ⁇ m or less from the viewpoint of dispersibility with respect to the resin composition and workability of an adhesive film and a coverlay film prepared using the resin composition.
• a filler when included as the component (F), a filler that has been subjected to a surface treatment as necessary may be used.
• a filler include those in which an oxide film is formed on the particle surface.
• Component (G) Organic Peroxide
• the resin composition of the present invention comprises an organic peroxide as component (G) in addition to the above components (A) to (E) (may contain component (F)). You may contain a thing. Reaction of the vinyl compound used as the component (A) at the time of heat curing of the adhesive film and coverlay film prepared using the resin composition of the present invention by containing an organic peroxide as the component (G) Is promoted.
• the organic peroxide of component (G) includes benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di (3,5,5- Diacyl peroxides such as trimethylhexanoyl) peroxide; peroxyketals such as 2,2-di (4,4-di- (di-tert-butylperoxy) cyclohexyl) propane; isopropyl purge carbonate, di-sec Peroxydicarbonates such as butyl purge carbonate, di-2-ethylhexyl purge carbonate, di-1-methylheptyl purge carbonate, di-3-methoxybutyl purge carbonate, dicyclohexyl purge carbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-e
• tert-butyl peroxybenzoate has an optimum activation temperature, that is, a temperature range of 60 to 120 ° C. in the drying process of film formation, and around 80 ° C. at the time of transfer of an adhesive film or a coverlay film. It is not activated in the above temperature range, but it is activated in the temperature range of 180 to 210 ° C. during the heat curing of the adhesive film or coverlay film, and the shelf life of the adhesive film or coverlay film is good. preferable.
• component (G) When an organic peroxide is contained as the component (G), the content in the resin composition of the present invention is as follows: Component (A), Component (B), Component (C), Component (D), Component (E) , (If included, component (F)) and 100 parts by mass of component (G), preferably 5 parts by mass or less, more preferably 3 parts by mass or less, More preferably, it is ⁇ 1 part by mass.
• the resin composition of the present invention may contain components other than the above components (A) to (G) as necessary.
• Specific examples of such components include silane coupling agents, antifoaming agents, flow control agents, film forming aids, dispersants, and the like.
• the resin composition of the present invention can be produced by a conventional method. For example, in the presence or absence of a solvent, the above components (A) to (E) (if the resin composition contains the above components (F), (G) and other optional components, these optional Ingredients) are mixed with a heating vacuum mixing kneader.
• the resin composition contains the above components (F), (G) and other optional components, these optional components) so that the above components (A) to (E) have a desired content ratio , Dissolved in a predetermined solvent concentration, put them in a reaction kettle heated to 10 to 80 ° C., mixed at atmospheric pressure for 3 hours while rotating at a rotational speed of 100 to 1000 rpm, The mixture can be further stirred for 30 to 60 minutes at (maximum 1 Torr).
• the adhesive film and coverlay film of the present invention can be obtained from the resin composition of the present invention by a known method.
• the resin composition of the present invention is diluted with a solvent to obtain a varnish, which is applied to at least one side of a support and dried, and then provided as a film with a support or a film peeled from the support. be able to.
• the solvent that can be used as the varnish examples include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; high-boiling solvents such as dioctyl phthalate and dibutyl phthalate.
• the amount of the solvent used is not particularly limited and may be a conventionally used amount, but is preferably 20 to 90% by mass with respect to the solid content.
• the support is appropriately selected depending on the desired form in the film production method, and is not particularly limited. Examples thereof include metal foils such as copper and aluminum, and carrier films of resins such as polyester and polyethylene. When providing the adhesive film of this invention as a form of the film peeled from the support body, it is preferable that the support body is mold-release-processed with the silicone compound etc.
• the method for applying the varnish is not particularly limited, and examples thereof include a slot die method, a gravure method, a doctor coater method, and the like, which are appropriately selected according to a desired film thickness and the like. This is preferable because it can be designed to be thin.
• coating is performed so that the thickness of the film formed after drying may turn into desired thickness. Such a thickness can be derived from the solvent content by those skilled in the art.
• the thickness of the adhesive film and cover lay film of the present invention is appropriately designed based on characteristics such as mechanical strength required according to the application, but is generally 1 to 100 ⁇ m, and when thinning is required, It is preferably 1 to 30 ⁇ m.
• the drying conditions are appropriately designed according to the type and amount of the solvent used in the varnish, the amount of varnish used and the thickness of the coating, and are not particularly limited, but are, for example, 60 to 120 ° C., It can be performed under atmospheric pressure.
• the adhesive film and coverlay film of the present invention before use are stored in a state of being sandwiched between protective films in order to prevent foreign matter from adhering.
• a protective film what was described as a base material can be used.
• the procedure for using the adhesive film of the present invention is as follows.
• the adhesive film of the present invention is placed on the surface to be bonded of one object, the other surface is exposed to the adhesive film. Place it in contact with the surface.
• the adhesive film is placed so that the exposed surface of the adhesive film is in contact with the adherend surface of one object, and the adhesive film is transferred onto the adherend surface.
• the temperature at the time of transfer can be set to 80 ° C., for example.
• the other object is placed on the surface of the adhesive film exposed by peeling the support during transfer so that the surface to be bonded is in contact with the exposed surface of the adhesive film.
• thermocompression bonding is performed for a predetermined temperature and for a predetermined time, and then heat-cured.
• the temperature during thermocompression bonding is preferably 100 to 200 ° C.
• the time for thermocompression bonding is preferably 0.5 to 10 minutes.
• the temperature for heat curing is preferably 180 to 210 ° C.
• the heat curing time is preferably 30 to 120 minutes.
• the procedure for using the coverlay film of the present invention is basically the same. After the coverlay film of the present invention is placed at a predetermined position on the printed wiring board, that is, at a position covered with the coverlay film, a predetermined temperature is set. Then, it may be heat-pressed for a predetermined time, and then heat-cured.
• a varnish obtained by diluting the resin composition of the present invention with a solvent is applied to the surface to be bonded (position to be covered with a film in the case of a coverlay film). After applying and drying, the above-described procedure of placing one object (in the case of a coverlay film, thermocompression bonding) may be performed.
• the adhesive film and coverlay film of the present invention are excellent in high frequency electrical characteristics after heat curing.
• the heat-cured coverlay film preferably has a dielectric constant ( ⁇ ) of 3.0 or less, more preferably 2.5 or less, in a frequency range of 1 to 10 GHz.
• the dielectric loss tangent (tan ⁇ ) in the frequency region of 1 to 10 GHz is more preferably 0.01 or less, and more preferably 0.0025 or less.
• the adhesive film and coverlay film of the present invention have sufficient adhesive strength after heat curing.
• the adhesive film and the coverlay film after heat curing preferably have a peel strength (180 degree peel) with respect to the roughened surface of the copper foil measured in accordance with JIS C6471 of 5 N / cm or more, more preferably. Is 8 N / cm or more, more preferably 10 N / cm or more.
• the adhesive film and coverlay film of the present invention have sufficient flame retardancy after heat curing. Specifically, it is preferable that the adhesive film and the coverlay film after heat curing pass with a flame retardancy class V-0 in a flame retardancy test performed in accordance with the flame retardancy standard of UL94V. Moreover, it is preferable that the adhesive film and coverlay film after heat curing pass with the flame retardancy class VTM-0 in the flame retardancy test conducted in accordance with the flame retardancy standard of UL94VTM.
• Examples 1 to 12, Comparative Examples 1 to 6) Mix each component so that the blending ratio (parts by mass) shown in the table below is met, add toluene, put into a reaction kettle heated to 80 ° C., and mix at normal pressure while rotating at 150 rpm. For 3 hours.
• the varnish containing the resin composition thus obtained was applied to one side of a base material (PET film subjected to release treatment) and dried at 100 ° C. to obtain an adhesive film with a support.
• the abbreviations in the table represent the following.
• Ingredient (A) OPE2200: Oligophenylene ether (vinyl compound represented by the above general formula (1)) (Mn 2200), manufactured by Mitsubishi Gas Chemical Co., Ltd.
• Ingredient (E) OP935 Aluminum organophosphinate, manufactured by Clariant Japan
• Ingredient (E ') FP2200 Phosphate flame retardant, ADEKA Corporation
• PX-200 Phosphate ester flame retardant, manufactured by Daihachi Chemical Industry
• Ingredient (F) SE2050 Silica filler, Admatechs Co., Ltd.
• KBM403 Silane coupling agent, Shin-Etsu Chemical Co., Ltd.
• DISPERBYK2009 Dispersant, manufactured by Big Chemie Japan
• Dielectric constant ( ⁇ ), dielectric loss tangent (tan ⁇ ) After the adhesive film was cured by heating at 180 ° C. and peeled from the support, a test piece (40 ⁇ 0.5 mm ⁇ 100 ⁇ 2 mm) was cut out from the adhesive film, and the thickness was measured. The test piece was rolled into a cylindrical shape having a length of 100 mm and a diameter of 2 mm or less, and a dielectric constant ( ⁇ ) and a dielectric loss tangent (tan ⁇ ) were measured by a cavity resonator perturbation method (10 GHz).
• Glass transition point Tg measured by dynamic viscoelasticity measurement (DMA). After the adhesive film was heat-cured at 180 ° C. and peeled from the support, a test piece (10 ⁇ 0.5 mm ⁇ 40 ⁇ 1 mm) was cut out from the adhesive film, and the width and thickness of the test piece were measured. Thereafter, measurement was performed with DMS6100 (3 ° C./min 25-220 ° C.). The peak temperature of tanD was read and used as Tg.
• DMA dynamic viscoelasticity measurement
• Linear expansion coefficient Measured with a thermal analyzer (TMA). After the adhesive film was heat-cured at 180 ° C. and peeled off from the support, a test piece (5 ⁇ 0.5 mm ⁇ 20 ⁇ 1 mm) was cut out from the adhesive film and measured with TMA4000S (5 ° C./min 25 ⁇ 230 ° C.). 90-100 ° C. C.I. T.A. The average of E was ⁇ 1, C.C. T.A. The average of E was ⁇ 2.
• test piece 50 ⁇ 0.5 mm ⁇ 200 ⁇ 0.5 mm
• the test piece was rolled into a cylindrical shape having a length of 200 mm and a diameter of about 15 mm and fixed to a stand.
• the flame of the gas burner was adjusted to a height of about 20 mm, and after burning for 3 seconds at the lower end of the film, the burning time was measured.
• Varnish stability The varnish containing the resin composition obtained by the above procedure was sealed in a glass bottle and allowed to stand at 25 ° C., and the stability of the solution was confirmed. The number of days until the generation of crystals, precipitates, separation of the solution, etc. were compared, and those that were stable for one week or more were marked with ⁇ and those with about 3 days were marked with ⁇ .
• Solubility The varnish containing the resin composition obtained by the above procedure was allowed to stand at room temperature. The resin composition components were not recrystallized.
• Example 1 a uniform adhesive film was obtained, and the embedding property at the time of thermocompression bonding was excellent. Further, the adhesive film was excellent in all of the high frequency electric characteristics (dielectric constant ⁇ , dielectric loss tangent Tan ⁇ ), peel strength, and flame retardancy after heat curing. Moreover, the solubility and stability of the varnish were also excellent.
• Comparative Example 1 in which the content of the component (E) is less than 10 parts by mass, the flame resistance of the obtained adhesive film was inferior.
• Comparative Example 2 in which the content of the component (E) exceeds 50 parts by mass, a mottled pattern occurred during film formation. Moreover, the embedding property at the time of thermocompression bonding of the obtained adhesive film was inferior.
• the stability of the varnish was also inferior.
• Comparative Example 3 using a phosphate-based flame retardant instead of the component (E) the obtained adhesive film had poor flame retardancy.
• Comparative Example 4 using a phosphate ester-based flame retardant instead of the component (E) the obtained adhesive film had poor flame retardancy.
• Comparative Example 5 in which a phosphate-based flame retardant was used in place of the component (E) and the blending amount of the flame retardant was increased the flame resistance of the obtained adhesive film was excellent. Occasionally mottled patterns occurred.
• the embedding property at the time of thermocompression bonding of the obtained adhesive film was inferior.
• the stability of the varnish was also inferior.

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• 2012
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