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WO2008105563A1 - Composition de résine adhésive ignifuge et matériau de panneau flexible imprimé utilisant celle-ci - Google Patents

Composition de résine adhésive ignifuge et matériau de panneau flexible imprimé utilisant celle-ci Download PDF

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Publication number
WO2008105563A1
WO2008105563A1 PCT/JP2008/054005 JP2008054005W WO2008105563A1 WO 2008105563 A1 WO2008105563 A1 WO 2008105563A1 JP 2008054005 W JP2008054005 W JP 2008054005W WO 2008105563 A1 WO2008105563 A1 WO 2008105563A1
Authority
WO
WIPO (PCT)
Prior art keywords
general formula
resin composition
hydrogen atom
retardant adhesive
flame
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.)
Ceased
Application number
PCT/JP2008/054005
Other languages
English (en)
Japanese (ja)
Inventor
Shigeaki Tauchi
Naoki Yokoyama
Tetsunori Satou
Katsuyuki Aida
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.)
Tohto Kasei Co Ltd
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Tohto Kasei Co Ltd
Nippon Steel Chemical Co Ltd
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 Tohto Kasei Co Ltd, Nippon Steel Chemical Co Ltd filed Critical Tohto Kasei Co Ltd
Priority to JP2009501333A priority Critical patent/JP5334127B2/ja
Publication of WO2008105563A1 publication Critical patent/WO2008105563A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions 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
    • 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
    • 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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • 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

Definitions

  • the present invention relates to a heat-resistant adhesive resin composition, and more specifically, a high heat-resistant and flame-retardant adhesive composition substantially free of halogen elements, an adhesive film using the same, a force parlay film, and flexible copper
  • the present invention relates to a flame-retardant adhesive resin composition suitable for a flexible printed circuit board (hereinafter also referred to as FPC).
  • FPC flexible printed circuit board
  • a base material such as paper-phenol resin, glass fiber-epoxy resin, a polyimide film, a polyethylene terephthalate film, or the like and a metal bonded to each other have been used.
  • a printed wiring board refers to a laminate before circuit processing
  • a circuit processed from this metal foil is referred to as a printed wiring board, and both are referred to as printed boards.
  • Such adhesives are widely used as adhesives for multilayer printed circuit boards and adhesives for force parlay films, but materials with excellent adhesive strength, chemical resistance, solder heat resistance, folding resistance, etc. Has come to be required. In addition, materials with excellent flame retardancy have been demanded from the viewpoint of ensuring fire safety.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 10-1 0 20 25
  • Patent Document 2 Japanese Patent Laid-Open No. 200 1-1 64 2 26
  • Patent Document 3 Japanese Patent Application Laid-Open No. 200 1-3 23 242
  • Patent Document 4 Japanese Laid-Open Patent Publication No. 200 1-3549 3 6
  • Patent Document 5 Japanese Patent Laid-Open No. 2003-3 1 8 1 9 93
  • All of the above patent documents are mainly composed of epoxy resin, curing agent, acrylonitrile butadiene rubber or phenoxy resin, and all flame retardant means are fluorinated epoxy resin, brominated phenoxy. By blending rosin.
  • Patent Document 6 Japanese Patent Application Laid-Open No. 200 1-3 3 9 1 3 1
  • Patent Document 7 Japanese Patent Application Laid-Open No. 200 2-6 0 720
  • Patent Document 8 Japanese Laid-Open Patent Publication No. 2000-3 1 764 70
  • Patent Document 9 Japanese Unexamined Patent Application Publication No. 2004-3 3 1 7 8 3
  • Patent Document 10 JP-A-2005-290229
  • Patent Documents 6, 7, and 9 blend organic phosphorus compounds, and Patent Documents 8 and 10 blend known phosphorus-containing epoxy resins and phosphorus-containing phenoxy resins as non-halogen flame retardant means, respectively. I am going to do that. Disclosure of the invention An object of the present invention is to provide a flame retardant adhesive resin composition which is excellent in adhesive properties such as peel adhesive strength, solder heat resistance, flowability, etc., and which is non-halogenated to cope with the environment. Furthermore, it is to provide a flame retardant adhesive film, a coverlay film and a flexible copper clad laminate using such an adhesive resin composition.
  • the present inventors have used the specific resin in the adhesive resin composition and found specific components, thereby completing the present invention.
  • the present invention provides the following components (ii) to (2):
  • X is selected from the following general formula (2), (3), (4) or (5), which requires a divalent group represented by the following general formula (2) or (3) Represents at least one divalent group, Z represents a hydrogen atom or the general formula (6), and n is an average value of 21 or more.
  • Y represents a phosphorus-containing group represented by the general formula (7) or (8), and scales R i to R 4 , R! To ⁇ 4 , R i Rs independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
  • A is a single bond or one CH 2 —, one C (CH 3 ) 2 —, —CH (CH 3 ) one, one S—, — S 0 2 —, one O—, one CO— or general formula (9)
  • RR s independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
  • W represents a divalent group represented by the general formula (5), m is an integer of 0 or more, and the average of m is 0.1 to 15.
  • This is a flame retardant adhesive resin composition characterized by the above.
  • the present invention provides that the component (i) is a divalent group represented by the general formulas (2) and (5) in the general formula (1), and Ri Rg in the general formula (2) is hydrogen May be characterized in that Y represents the general formula (7) and Ri Rs in the general formula (5) represents a hydrogen atom, but A represents --C (CH 3 ) 2- (I)
  • X is a divalent group represented by the general formulas (3) and (5), and Ri Rs in the general formula (3) represents a hydrogen atom.
  • Y represents the general formula (7)
  • Ri Rs in the general formula (5) represents a hydrogen atom, but A may represent one C (CH 3 ) 2 —, or ( Ii)
  • X is a divalent group represented by the general formulas (2) and (5)
  • Ri Rs in the general formula (2) represents a hydrogen atom
  • Y is Shows the general formula (7)
  • Ri Rs represents a hydrogen atom, but A may be characterized by the general formula (9), or (i) the component is the general formula (1), and X is It is a divalent group represented by general formulas (3) and (5).
  • R to Shaku 3 represents a hydrogen atom, but Y represents general formula (7).
  • R i Rs in the formula (5) represents a hydrogen atom, but A may be characterized by the general formula (9).
  • the flame retardant adhesive resin composition of the present invention may contain 20 to 80 parts by weight of component (i) with respect to 100 parts by weight of the composition.
  • the flame-retardant adhesive film of the present invention is characterized in that the flame-retardant adhesive resin composition of the present invention is formed into a film.
  • the force parlay film of the present invention is characterized by having a polyimide film and a layer made of the flame-retardant adhesive resin composition of the present invention provided on the polyimide film.
  • the flexible copper-clad laminate of the present invention is characterized by having a polyimide film, a layer made of the flame-retardant adhesive resin composition of the present invention provided on the film, and a copper foil. Is.
  • the flame-retardant adhesive resin composition of the present invention (sometimes abbreviated as an adhesive resin composition or a resin composition) contains the above components (i) to (2) as essential components.
  • the component is a phosphorus-containing phenoxy resin
  • the component is an epoxy resin
  • the component is a curing agent
  • the component is a curing accelerator, and substantially contains a halogen element. Not included.
  • substantially free of halogen elements means that no halogen and halogen compounds of 90 Owtppm or more are contained as halogen elements.
  • component Li emissions containing phenoxy resin is represented by the general formula (1), a re-emission content of 1 wt% to 6 wt. 0/0, and using gel permeation chromatography to emissions chromatography
  • the measured standard polyethylene oxide-converted weight average molecular weight is 60, 00 0 to 20 0, 0 0 0, preferably 70, 00 0-1 3 0, 0 0 0, more preferably 8 0, 0 0 0 Use one that is ⁇ 1 2 5, 0 0 0.
  • X is the above general formula (2), (3),
  • one or both of the divalent groups represented by the general formula (2) or (3) is 20 mol 0 / in X. Or more, preferably 50 mol% or more It is good to include.
  • Z represents a hydrogen atom or a glycidyl group represented by the above formula (6).
  • n is an average value of 2 1 or more, but is preferably in the range of 30 to 500.
  • Such a phosphorus-containing phenoxy resin can be produced, for example, by the method disclosed in Japanese Patent Application Laid-Open No. 2000-310.
  • Y represents a phosphorus-containing group represented by the general formula (7) or (8).
  • a in formula (5) is a single bond or one CH 2 —, one C (CH 3 ) 2 —, one CH (CH 3 ) one, one S—, one S 0 2 —, ten thousand, one CO— Or a divalent group selected from the above general formula (9).
  • Ri Ri in Formula (2)-(5) and (7)-(9) Independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Preferably, they are a hydrogen atom or a methyl group, and the number of methyl groups is 4 or less.
  • component (i) is a divalent group represented by the above general formulas (2) and (5) in the above general formula (1)
  • R Rg in the general formula (2) is a hydrogen atom
  • Y represents the general formula (7)
  • R to 8 in the general formula (5) represent a hydrogen atom, but A may represent —C (CH 3 ) 2 —.
  • component (i) is a divalent group represented by the general formulas (3) and (5) in the general formula (1), and Ri Rs in the general formula (3) represents a hydrogen atom.
  • Ri Rs in the general formula (3) represents a hydrogen atom.
  • Y represents the general formula (7), and R to 8 in the general formula (5) represent a hydrogen atom, but A may represent —C (CH 3 ) 2 —.
  • component (i) is a divalent group represented by the general formulas (2) and (5) in the general formula (1), and R i Rs in the general formula (2) represents a hydrogen atom.
  • Y represents the general formula (7)
  • R 1 to R 8 in the general formula (5) is a hydrogen atom, may be one a represents the general formula (9).
  • component (i) is a divalent group represented by the general formulas (3) and (5) in the general formula (1), and Ri Rg in the general formula (3) represents a hydrogen atom.
  • Y represents the general formula (7), Ri to R 8 in the general formula (5) represent a hydrogen atom, but A represents the general formula (9) Five
  • the component epoxy resin is an epoxy resin represented by the above general formula (10).
  • W represents a divalent group represented by the general formula (5)
  • m is an integer of 0 or more
  • the average of m is 0 ⁇ 1 to 15.
  • Examples of the epoxy resin represented by the general formula (10) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, and the like. May be used alone or in combination of two or more. It is preferable that the epoxy resin does not substantially contain a haguchigen element.
  • the component (ii) is 20 to 80 parts by weight, preferably 30 to 70 parts by weight, more preferably 40 to 6 parts by weight. It is preferable to add 0 part by weight. If the amount is less than 20 parts by weight, the adhesiveness does not develop due to a decrease in flexibility and the stress at the buttock.If the amount exceeds 80 parts by weight, the soldering heat resistance decreases due to a decrease in the ratio of the cross-linking component, and the adhesive. As the performance is impaired.
  • the (mouth) component is preferably blended in the range of 20 to 70 parts by weight. (Mouth) If the component is less than this range, the crosslink density will decrease and the heat resistance of the adhesive will decrease. On the other hand, if it is too high, the flexibility of the adhesive will decrease and the adhesive will The problem arises that the peel adhesion is reduced.
  • Component curing agents that are known as (mouth) component epoxy resin curing agents can be used, such as nopolac-type phenolic resin, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, azines, Imidazoles, acid anhydrides, etc. can be used.
  • imidazole is used as component (c)
  • it is also calculated as component (2) because it is also component (2).
  • the amount of ingredient used is (mouth) ingredient It is preferable to blend such that the equivalent ratio ((C) / (Mouth)) of the epoxy resin is 0.5 to 1.5. In general, when using a phenol resin curing agent, 0.8 to 1.
  • an amine curing agent When an amine curing agent is used, it is preferably 0.5 to 1.0.
  • organophosphorus compounds such as triphenylphosphine, imidazoles such as 2-phenylimidazole and 2-ethyl-4-methylimidazole, tertiary amines, and Lewis acids can be used.
  • the blending ratio is appropriately selected according to the required curing time. Generally, however, the blending ratio for the flame-retardant adhesive resin composition is from 0.01 to
  • the glass transition temperature (Tg) of a cured product obtained by thermosetting the flame retardant adhesive resin composition of the present invention is preferably 100 ° C. or higher, more preferably 100 to 1700. It should be in the range of ° C. When the glass transition temperature of the cured product after heat curing is less than 100 ° C, the migration resistance is lowered.
  • the glass transition temperature after curing of the resin composition can be adjusted mainly by the type and amount of the (mouth) component epoxy resin and (c) component curing agent.
  • the measurement of the glass transition temperature of the cured product is based on the conditions of the property evaluation method described later: ⁇ cured product properties> [glass transition temperature (Tg)]
  • the flame-retardant adhesive resin composition of the present invention includes, as components other than the above essential components, aluminum hydroxide and magnesium hydroxide as inorganic flame retardants, silica as a scavenger or extender, An extender such as calcium carbonate and a polymer elastomer can be blended as a flexibility-imparting agent, or additives such as a viscosity modifier and a coupling agent can be blended. The addition rate is appropriately selected according to the required characteristics.
  • the flame-retardant adhesive resin composition of the present invention is used as an adhesive resin solution dissolved or dispersed in an organic solvent such as methyl ethyl ketone, dimethylformamide, 2-ethoxyethanol or the like. .
  • an organic solvent such as methyl ethyl ketone, dimethylformamide, 2-ethoxyethanol or the like.
  • the solid content concentration is appropriately selected depending on use conditions, but is generally 20 to 60% by weight.
  • the solvent is not a component constituting the flame retardant adhesive resin composition of the present invention, but a component used to make the flame retardant adhesive resin composition into a solution. Therefore, the amount of each component in the flame retardant adhesive resin composition Solvents are excluded from the calculation.
  • the flame retardant adhesive resin composition of the present invention can be used after being formed into a film.
  • a flame retardant adhesive resin composition is diluted with an organic solvent such as methyl ethyl ketone. Then, the obtained adhesive resin solution is applied to a base material such as a metal foil, a polyester film, or a polyimide film whose surface has been peeled off by a conventionally known method, and the solvent is evaporated.
  • the composition constituting the adhesive resin layer is dried at a temperature and time conditions that do not cause a curing reaction to form an adhesive film layer, which is peeled off from the base material, and the flame retardant adhesive film And
  • the drying conditions vary depending on the solvent and resin composition used, but generally, a temperature of 130 to 160 ° C. and a temperature and time range of 3 to 10 minutes are selected.
  • the ratio of the thickness of the release film and the adhesive film layer is not particularly limited, but the release film thickness 1 2
  • An adhesive layer having 15 to 30 m provided at 5 / m can be suitably used.
  • Examples of the method of using the flame retardant adhesive film of the present invention include, for example, a flexible printed wiring board, a glass fiber-epoxy wiring board, a paper-phenol wiring board, and various printed wiring boards obtained by processing these circuits. Suitable for bonding objects such as metals and resin substrates.
  • a printed wiring board can be obtained by bonding a metal foil and a resin substrate, and a multilayer printed wiring board or printed wiring board can be obtained by bonding printed wiring boards or printed wiring boards together. By attaching the wiring board and force parlay, a printed wiring board with a coverlay can be obtained.
  • it can be used as an adhesive film for connecting printed wiring boards or printed wiring boards. In any case, it is advantageously used in the process of manufacturing or processing printed circuit boards.
  • the flame retardant adhesive resin composition of the present invention can also be applied to the adhesive layer of a force parlay film.
  • the cover lay film is formed from the polyimide film and the above adhesive resin composition.
  • a method of forming the force parlay film of the present invention It is possible to form a film using a conventional method.
  • the adhesive resin composition is diluted with an organic solvent such as methyl ethyl ketone to form a solution, and then the obtained adhesive resin solution is applied onto a polyimide film.
  • the polyimide film is coated with a thickness of 2 to 200 m, preferably 5 to: 100 ⁇ m ⁇ , more preferably 10 to 50 ⁇ m, and then dried.
  • the drying conditions vary depending on the solvent and resin composition used, but generally, a temperature of 130 to 160 ° C, 3 to: L 0 minutes, and a time range are selected.
  • Polyimide film is necessary to increase heat resistance and flame retardancy.
  • the thickness of this polyimide film may be an appropriate thickness as required, but preferably 3 to 50 0 iim, more preferably 5 to 30 / zm.
  • the thickness ratio between the polyimide film and the adhesive layer is not limited, but the film thickness is 1 2.5 5 111 to the adhesive layer 1 5 to 20 m, the film thickness is 25 im to the adhesive layer 2 5 to 3 5 ⁇ m, each of which a force-parlay film is provided.
  • the flame-retardant adhesive resin composition of the present invention can also be applied to an adhesive layer of a flexible copper-clad laminate (hereinafter also referred to as a three-layer copper-clad laminate).
  • the flexible copper clad laminate is formed from a polyimide film, the adhesive resin composition, and a copper foil.
  • a method for forming the flexible copper clad laminate of the present invention a conventional method is used. Can be stacked.
  • the adhesive resin composition is diluted with an organic solvent such as methyl ethyl ketone to form a solution, applied to one or both sides of a polyimide film, and the organic solvent content is dried.
  • the drying conditions vary depending on the solvent and resin composition used, but in general, a temperature of 130 to 160 ° C, a temperature of 3 to 10 minutes and a time range are selected. In general, the temperature is selected from the range of temperature and time from 160 to 190, and from 10 to 120 minutes.
  • the thickness of the polyimide film layer, the adhesive layer and the copper foil is not particularly limited, but the polyimide film thickness is 5 to 25 ⁇ , and the adhesive layer 1 Generally, the thickness is 0 to 30 ⁇ m and the copper foil thickness is 10 to 35 m.
  • the temperature dispersion tan ⁇ curve of this sample was measured using a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments Inc., DM S _ 6 1 0 0), with a frequency of 10 ⁇ ⁇ and a temperature range of 1 5 0 to 2 0 The measurement was carried out under the conditions of 0 ° C. and a heating rate of 2 ° C./min.
  • the peak temperature of the obtained temperature-ta ⁇ ⁇ curve was defined as the glass transition temperature (T g).
  • JP CA—BM0 2-1 9 9 1 was cut to the dimensions described in 7.7 and the two force parlay films were bonded together on the adhesive surface. Thereafter, the sample was prepared by heating and pressing at 170 ° C. for 1 hour, and then post-curing at 190 ° C. for 2 hours. Subsequently, according to the procedure of JPCA-BM0 2— 1 9 9 1 7.7, fire resistance test and fire resistance measurement, UL standard 94 criteria “VTM-0”, “flame resistance” The flame resistance was judged based on two levels of “None”. “VTM-0” means flame resistance.
  • test piece After preparing the coverlay film under the same conditions as described above, the test piece was prepared and the peel strength was measured in accordance with the peel strength of 75 of JPCA—BM02-19-191.
  • the test piece adhesive was thermally cured in the same manner at 170 ° 0 for 1 hour, followed by heating and post-curing at 190 ° C for 2 hours.
  • test piece After preparing a force parlay film under the same conditions as described above, a test piece was prepared and a solder heat resistance test was performed in accordance with the solder heat resistance (appearance) of JP CA—BM0 2 — 1 9 9 1—7.9.
  • the adhesive thermosetting conditions at the time of test piece preparation were the same as described above: after 1 hour of heating press at 170 ° C., followed by post curing at 190 ° C. for 2 hours. After drying this test piece at 105 for 1 hour, the test piece was floated in a solder bath set to each evaluation temperature for 5 seconds. Observations were made to check for defects such as foaming, blistering, and peeling. “300 ° C” in the table means that no defects are observed when evaluated in a 300 ° C solder bath.
  • test piece and folding resistance test were conducted according to the A method folding resistance test of 7.6.1.
  • the curing conditions were similarly set at 170 ° C. for 1 hour after heat-pressing the power parlay film, followed by post curing at 190 ° C. for 2 hours.
  • the radius of curvature was 0.38 mm.
  • Judgment is based on measuring the number of bends until the sample copper circuit is disconnected and the current cannot be supplied. If the number of bends before disconnection is 1 00 0 0 or more and less than 3 0 0 0 0, “OK”, 3 0 0 A case of zero or more was judged as “good”.
  • test piece preparation and adhesive flow test were performed according to JPCA—BM0 2 — 1 9 9 1 — 7.10. The determination was made by measuring the length of the adhesive that had oozed out.
  • a comb-like circuit pattern was obtained by etching the copper foil of a single-sided copper-clad laminate so that the circuit line / space was 100 ⁇ m / 200 ⁇ m.
  • the sample was prepared by post-curing the cover lay film for 1 hour at 1700 and after heating for 2 hours at 190. Place the sample in a constant temperature and humidity chamber adjusted to 85 ° C—85% RH%, energize 50 V DC for 50 hours in the comb circuit in the sample, and then remove the sample. The comb circuit and its surroundings are observed with a microscope. If dendrites are observed, The case where it was not recognized was judged as “good”.
  • the peel strength was measured according to JISC 64 7 1 Measured according to
  • the bondinda sheet was peeled off from the release film. 1 Precured at 70 ° C for 1 hour and postcured at 190 ° C for 2 hours. Was prepared. A through hole with a diameter of 0 to 3 mm was drilled in this cured sheet, and a copper plating layer of 20 to 25 / zm was formed inside the hole by an electroless plating method to prepare a sample. Expose the sample to a heat cycle of 40 ° C ⁇ 15 minutes, 1 50 ° C ⁇ 15 minutes, measure the number of cycles until poor continuity occurs. 0 0 0
  • V-0 means flame resistance
  • the peel strength of the copper foil layer and the insulating resin layer in the three-layer copper-clad laminate prepared under the same conditions as described above was measured according to JI S C 64 71.
  • the folding resistance of a three-layer copper-clad laminate prepared under the same conditions as described above was measured according to JIS C 64 71.
  • the radius of curvature was 0.8 mm. Judgment was made by measuring the number of flexing cycles until the sample copper circuit was disconnected and could not be energized.
  • phosphorus-containing phenol represented by the following formula (1 1): 1 0— (2,5-Dihydroxyphenol-Nole)-1 0 H— 9—Oxa 1 0—Phosphaphenanthrene 1 0 H— 9-Oxide (manufactured by Sanko Chemical Co., Ltd., HCA-HQ, hydroxyl equivalent 16 2 g / eq, phosphorus content 9.5 wt%) 16 2 parts, bisphenol A type epoxy resin (Toto Kasei Co., Ltd.) YD—8 1 2 5, made by company, epoxy equivalent 1 7 1.
  • a phosphorus-containing phenoxy resin was synthesized in the same manner as in Synthesis Example 1 except that the reaction time in Synthesis Example 1 was changed from 8 hours to 10 hours. B was obtained. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 109,700.
  • the phosphorus-containing phenoxy resin was synthesized in the same manner as in Synthesis Example 1, except that the reaction time in Synthesis Example 1 was changed from 8 hours to 20 hours. C was obtained.
  • the standard polyethylene oxide equivalent weight average molecular weight of the resin was 19.8,400.
  • Bisphenol A type epoxy resin in synthesis example 1 (manufactured by Tohto Kasei Co., Ltd., YD_ 8 1 2 5, epoxy equivalent 1 7 1.
  • S g / eq) is replaced by the following formula (1 3)
  • Bisphenol fluorene type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., ER F—300, epoxy equivalent 2 3 1 gZ e ci) was used, and the reaction time in Synthesis Example 1
  • the phosphorus-containing phenoxy resin E was synthesized by synthesizing the phosphorus-containing phenoxy resin in the same manner as in Synthesis Example 1 except that the value was changed from 8 hours to 10 hours. .
  • the standard polyethylene oxide equivalent weight average molecular weight of the resin was 1 17,000.
  • the phosphorus-containing phenoxy resin was synthesized in the same manner as in Synthesis Example 4, except that the reaction time in Synthesis Example 4 was changed from 10 hours to 5 hours. Got G. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 41,500.
  • YD-128 Bisphenol A type epoxy resin (manufactured by Toto Kasei)
  • YDF-170 Bisphenol F-type epoxy resin (manufactured by Toto Kasei Co., Ltd.)
  • BRG-555 Novolac-type phenolic resin (Showa Polymer Co., Ltd.)
  • Resin A Phosphorus-containing fuco-oxy resin A of Synthesis Example 1 (weight average molecular weight 7 7, 300)
  • Resin B Phosphorus-containing fuconoxy resin B of Synthesis Example 2 (weight-average molecular weight 1 0 9, 700)
  • Resin c Phosphorus-containing fuconoxy resin c of Synthesis Example 3 c (weight average molecular weight 1 9 8, 400)
  • Resin D Phosphorus-containing fuconoxy resin D of Synthesis Example 4 D (weight average molecular weight 1 2 2, 4 70)
  • Resin E Phosphorus-containing fuconoxy resin E in Synthesis Example 5 (weight average molecular weight 1 1 7, 900)
  • Resin F Lin-containing fuco-oxy resin F in Synthesis Example 6 (weight average molecular weight 3 9, 20 0)
  • Resin G Synthesis Lin-containing fuconinoxy resin G from Example 7 (weight average molecular weight 4 1, 500)
  • YP-50SC Phenoxy resin (manufactured by Tohto Kasei Co., Ltd.) (weight average molecular weight 5 0, 500)
  • PNR1H Carboxyl group-containing NBR (manufactured by JSR Corporation)
  • SPE-100 Cyclophenoxyphosphazene (Otsuka Chemical Co., Ltd.)
  • the GPC analysis of the epoxy resin was performed under the following conditions.
  • the adhesive resin composition was evaluated for cured product properties, FPC material properties (cover-lay film properties, bonding sheet properties, three-layer copper-clad laminate properties). The results are shown in Table 4.
  • the cover The flame resistance in the Rayfilm characteristics is VTM-0
  • the bond resistance in the bondinda sheet characteristics and the three-layer copper-clad laminate characteristics are V-0, both of which were confirmed to be flame retardant.
  • the solder heat resistance (drying) is 300 ° C or higher
  • the solder heat resistance (humidity resistance) is 2550 ° C or higher
  • the folding resistance is 2820 times or higher in the properties of force parlay film.
  • the folding resistance in the properties of copper-clad laminates is 150 times or more, and all show good physical properties.
  • the adhesive flow in force parlay film characteristics is 0.18 mm or less, showing good physical properties, no problem with migration resistance, and through-hole mesh conductivity in bonding sheet characteristics.
  • Examples 1 to 16 in particular, an FPC material using resin B having a molecular weight of 109,700, resin D having a molecular weight of 122,470, or resin E having a molecular weight of 117,900 The characteristics are excellent in both solder heat resistance and folding resistance.
  • Comparative Examples 1 and 2 show flame retardancy in the FPC material characteristics, but the solder heat resistance and folding resistance in the cover lay film characteristics are low, and the flowability of the adhesive is 0.8 mm or more. Lack of sex. In Comparative Examples 3 to 5, no flame resistance is observed in the FPC material characteristics.
  • Table 1 shows Examples 1 to 6
  • Table 2 shows Examples 7 to 12
  • Table 3 shows Examples 13 to 16
  • Table 4 shows Comparative Examples 1 to 5.
  • Folding resistance 3900 4400 5400 5600 Adhesive flow 0. 06 0. 08 0. 10 0. 10 My resistance; r Lacing property Good Good Good Ho, ent, inter, sheet, flame resistance V- 0 vo vo vo Characteristic tear strength
  • the adhesive resin composition of the present invention and the cover lay film, bonding sheet and three-layer copper-clad laminate using the same are non-halogen and flame retardant, and are effective in addressing environmental problems.
  • Excellent FPC characteristics such as foldability, migration resistance, and through-hole plating conduction reliability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

L'invention concerne une composition de résine adhésive ignifuge à utiliser pour un panneau flexible de montage. La composition contient, comme constituants essentiels, (a) une résine époxy spécifiée, (b) une résine phénoxy contenant du phosphore, spécifiée, (c) un agent de durcissement, et (d) un accélérateur de durcissement. La composition de résine adhésive ignifuge présente d'excellentes caractéristiques adhésives, comme une force adhésive au pelage élevée, une résistance élevée à la chaleur de soudage, une faible fluidité et similaire, tout en ne contenant aucun élément halogène.
PCT/JP2008/054005 2007-02-28 2008-02-28 Composition de résine adhésive ignifuge et matériau de panneau flexible imprimé utilisant celle-ci Ceased WO2008105563A1 (fr)

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WO2019065552A1 (fr) * 2017-09-26 2019-04-04 日鉄ケミカル＆マテリアル株式会社 Résine phénoxy contenant du phosphore, composition de résine correspondante et produit durci
CN116209667A (zh) * 2020-06-22 2023-06-02 多伦多大学管理委员会 香草醛衍生的阻燃单体、树脂、预聚物和聚合物

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JP5719574B2 (ja) * 2010-11-25 2015-05-20 新日鉄住金化学株式会社 リン含有フェノール樹脂、該樹脂組成物及び硬化物
TWI426116B (zh) * 2011-10-07 2014-02-11 Hong Tai Electric Ind Co Ltd 黏著劑組成物、黏著層及其積層結構
CN103059793A (zh) * 2011-10-20 2013-04-24 宏泰电工股份有限公司 粘着剂组合物、粘着层及其积层结构

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WO2019065552A1 (fr) * 2017-09-26 2019-04-04 日鉄ケミカル＆マテリアル株式会社 Résine phénoxy contenant du phosphore, composition de résine correspondante et produit durci
JPWO2019065552A1 (ja) * 2017-09-26 2020-10-15 日鉄ケミカル＆マテリアル株式会社 リン含有フェノキシ樹脂、その樹脂組成物、及び硬化物
JP7244427B2 (ja) 2017-09-26 2023-03-22 日鉄ケミカル＆マテリアル株式会社 リン含有フェノキシ樹脂、その樹脂組成物、及び硬化物
CN116209667A (zh) * 2020-06-22 2023-06-02 多伦多大学管理委员会 香草醛衍生的阻燃单体、树脂、预聚物和聚合物
EP4168419A4 (fr) * 2020-06-22 2024-07-10 The Governing Council of the University of Toronto Monomères ignifuges dérivés de vanilline, résines, prépolymères et polymères

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TWI445790B (zh) 2014-07-21
TW200902666A (en) 2009-01-16
JPWO2008105563A1 (ja) 2010-06-03

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