WO2013133240A1 - Adhésif imprimable et procédé associé de fabrication d'un corps assemblé - Google Patents

Adhésif imprimable et procédé associé de fabrication d'un corps assemblé Download PDF

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Publication number
WO2013133240A1
WO2013133240A1 PCT/JP2013/055905 JP2013055905W WO2013133240A1 WO 2013133240 A1 WO2013133240 A1 WO 2013133240A1 JP 2013055905 W JP2013055905 W JP 2013055905W WO 2013133240 A1 WO2013133240 A1 WO 2013133240A1
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WIPO (PCT)
Prior art keywords
adhesive
printing
adherend
heating
film
Prior art date
Application number
PCT/JP2013/055905
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English (en)
Japanese (ja)
Inventor
隆幸 米澤
改森 信吾
山本 正道
菅原 潤
淑文 内田
道廣 木村
聡志 木谷
幸枝 津田
木村 淳
Original Assignee
住友電気工業株式会社
住友電工プリントサーキット株式会社
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.)
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Application filed by 住友電気工業株式会社, 住友電工プリントサーキット株式会社 filed Critical 住友電気工業株式会社
Priority to CN201380012877.6A priority Critical patent/CN104185667B/zh
Priority to JP2014503848A priority patent/JP6033841B2/ja
Publication of WO2013133240A1 publication Critical patent/WO2013133240A1/fr

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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/0058Laminating printed circuit boards onto other substrates, e.g. metallic substrates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08Homopolymers or copolymers of acrylic acid esters
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/0277Bendability or stretchability details
    • H05K1/028Bending or folding regions of flexible printed circuits
    • H05K1/0281Reinforcement details thereof
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05Patterning and lithography; Masks; Details of resist
    • H05K2203/0502Patterning and lithography
    • H05K2203/0522Using an adhesive pattern
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/0091Apparatus for coating printed circuits using liquid non-metallic coating compositions

Definitions

  • the present invention when a reinforcing plate is bonded to a copper-clad laminate (CCL) or a flexible printed wiring board (FPC), or when an adhesive is applied to a portion other than a conductive portion of a substrate on which a conductive pattern is printed,
  • the present invention relates to a printing type adhesive capable of forming an adhesive application portion (pattern) by screen printing, and a method of manufacturing a joined body using the adhesive.
  • a flexible printed wiring board usually has a undulation on the coverlay film surface or base film surface due to a wiring pattern or the like. Moreover, as a cover-lay film, the hole for position alignment and another component mounting may be opened.
  • an adherend flexible print
  • a reinforcing plate 2 may be attached and bonded to a part of a wiring board or a copper-clad laminate) 1 in some cases.
  • FIG. 1B is a schematic plan view of a part of the flexible printed wiring board 1 in which the reinforcing plate 2 is bonded as viewed from the direction in which the reinforcing plate is installed.
  • FIG. 1A is a cross-sectional view of FIG. 1B. It is a schematic diagram.
  • 3 is an adhesive, and the reinforcing plate 2 is bonded to the flexible printed wiring board 1 via the adhesive 3.
  • a semi-cured film adhesive has been used for bonding a flexible printed wiring board or a copper-clad laminate and a reinforcing plate.
  • the film adhesive is cut out in a necessary shape in advance according to the portion to which the reinforcing plate is attached, and is stuck to the adhesive attachment position.
  • such a method is wasteful in cost because it discards the cut-out remaining portion of the film adhesive.
  • the film-like adhesive has adhesiveness in a semi-cured state, it is usually traded with a structure of a three-layer sheet sandwiched between release papers. For this reason, the provider of a film adhesive needs to produce such a three-layer sheet, and the cost of a separate member called release paper is required.
  • JP-A-4-77589 forms an adhesive layer by screen printing, and a flexible printed wiring board and a reinforcing board are provided. A bonding method for bonding has been proposed.
  • thermosetting epoxy-based adhesive having a controlled variation, specifically, a viscosity measured at a shear rate of 1 sec ⁇ 1 by dilution with a solvent.
  • Patent Document 1 Although an adhesive that can be screen-printed is proposed in Patent Document 1, there is no disclosure about a specific composition. On the other hand, when the adhesive composition used as a film adhesive is applied to screen printing instead of film formation, a film is produced such as chipping or bleeding of the printed portion, or poor plate separation. A new problem that did not exist when it occurred was simply unable to be diverted. In addition, in the case of an adhesive used for bonding a flexible printed wiring board or a copper-clad laminate and a reinforcing plate, there is a problem that required heat resistance and bonding strength are severe compared to simple printing ink. Cannot be diverted to adhesive
  • a conductive paste containing conductive particles for example, silver particles or the like
  • a substrate such as a flexible printed wiring board on which a conductive pattern is printed.
  • conductive particles for example, silver particles or the like
  • the present invention has been made in view of such circumstances, and an object of the present invention is a printing type adhesive capable of screen-printing an adhesive pattern, and further, heat resistance and bonding strength of a bonded portion. It is another object of the present invention to provide a printing adhesive capable of satisfying the above requirements, and a printing adhesive capable of high-level adjustment of a coating pattern such as printing only on a predetermined portion of an adherend.
  • the printing type adhesive of the present invention comprises (A) an acrylic resin having a weight average molecular weight (Mw) of 80,000 to 300,000, (B) an epoxy resin of 30 to 70% by mass of (A) the amount of acrylic resin, and (C) curing. (D) a printing type adhesive containing an inorganic filler having an average particle diameter of 1 ⁇ m or less, and (E) a solvent, and having a viscosity of 15 to 800 Pa ⁇ s at a rotation speed of 1 rpm as measured by an E type viscometer. The viscosity at a rotational speed of 50 rpm is 4 to 200 Pa ⁇ s. In addition, let said viscosity be the value measured at room temperature (25 degreeC).
  • the method for producing a joined body according to the present invention comprises a step of applying the printing adhesive of the present invention to the first adherend by screen printing and then heating at 100 to 250 ° C .; A step of placing two adherends; and a step of heating to 100 to 250 ° C. to thermally cure the adhesive application portion.
  • a method for producing a joined body wherein a transfer film obtained by applying and printing the above printing adhesive of the present invention on a release film by screen printing, and a first deposition.
  • the printing type adhesive of the present invention has a relatively high viscosity under a low shear rate and a low viscosity under a high shear rate, the adhesive can be applied by screen printing.
  • the printing type adhesive of the present invention comprises (A) an acrylic resin having a weight average molecular weight (Mw) of 80,000 to 300,000, (B) an epoxy resin of 30 to 70% by mass of (A) the amount of acrylic resin, and (C) curing. (D) a printing type adhesive containing an inorganic filler having an average particle diameter of 1 ⁇ m or less, and (E) a solvent, and having a viscosity of 15 to 800 Pa ⁇ s at a rotation speed of 1 rpm as measured by an E type viscometer. The viscosity at a rotational speed of 50 rpm is 4 to 200 Pa ⁇ s. In addition, let said viscosity be the value measured at room temperature (25 degreeC).
  • the (E) solvent is preferably an organic solvent having a boiling point of 160 ° C. or higher, and the content of the (E) solvent is preferably 55% by mass or less of the total amount of the printing adhesive.
  • the (C) curing agent preferably contains an acid anhydride, and the (D) inorganic filler is preferably contained in an amount of 1 to 30% by mass of the resin content.
  • the acrylic resin used in the present invention has a weight average molecular weight (Mw) of 80,000 to 300,000, preferably 100,000 to 200,000. This is because if the weight average molecular weight is less than 80,000, the heat resistance of the cured portion cannot be satisfied. On the other hand, if the weight average molecular weight exceeds 300,000, the melt viscosity of the adhesive increases, and even at a high shear rate, the viscosity is not sufficiently lowered, and stringing occurs during screen printing, resulting in poor plate separation. This is because irregularities are generated on the surface of the printed adhesive-applied portion, and as a result, voids are formed in the bonded portion, and the bonding strength may not be satisfied. In addition, when a solvent is added to lower the melt viscosity, the solid content concentration is lowered, and thick film printing may be difficult.
  • Mw weight average molecular weight
  • the acrylic resin is an acrylic ester or methacrylic ester (hereinafter referred to as “(meth) acrylic acid” unless the acrylic acid and methacrylic acid are particularly distinguished, and the ester is collectively referred to as “(meth) acrylate”). It is a polymer as a main constituent monomer.
  • Examples of the (meth) acrylic acid ester include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylate-n-butyl, methacrylate-n-butyl, acrylate isobutyl, methacrylate isobutyl, Isopentyl acrylate, isopentyl methacrylate, acrylic acid-n-hexyl, methacrylic acid-n-hexyl, isooctyl acrylate, isooctyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate Carbon number of (meth) acrylic acid such as methacrylic acid-n-octyl, isononyl acrylate, isononyl acrylate, acrylic acid-n-decyl, methacrylic acid-n-de
  • epoxy-containing (meth) acrylates such as glycidyl acrylate, glycidyl methacrylate, and acryl glycidyl ether; acrylic acid, methacrylic acid, itaconic acid, as long as the effects of the present invention are not impaired.
  • ⁇ , ⁇ -unsaturated carboxylic acids such as maleic acid and maleic anhydride
  • hydroxyl group-substituted (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate
  • amide-containing acrylics such as acrylamide and methacrylamide
  • vinyl monomers such as vinyl monomers, cyano group-containing acrylic monomers such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, vinyl acetate may be copolymerized.
  • Such an acrylic resin as a thermoplastic resin, softens and melts when heated, so that it flows into the concave portion of the adherend surface and the concave portion of the wiring pattern at the joining portion, and can be embedded in these concave portions.
  • the epoxy resin used in the present invention may be a resin having at least two epoxy groups in one molecule, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ether type epoxy resin, A glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a novolac type epoxy resin, a cresol novolak type epoxy resin and the like can be mentioned.
  • Epoxy resin is a thermosetting resin that contributes to the heat resistance and bonding strength of the joints and also contributes to ensuring insulation.
  • the epoxy resin is preferably contained in an amount of 30 to 70% by mass, preferably 30 to 55% by mass, based on the amount of the acrylic resin as component A. It is because heat resistance will fall when content of an epoxy resin decreases too much with respect to an acrylic resin. On the other hand, if the amount is too large, the acrylic resin becomes relatively small, so it becomes difficult to soften and melt at the time of heating and pressurization, and as a result, it becomes difficult to sufficiently fill the concave portion of the adherend, causing a decrease in bonding strength. Because it becomes.
  • (C) Hardener It is contained as a hardener for epoxy resins.
  • the curing agent polyamine curing agents, acid anhydride curing agents, boron trifluoride amine complex salts, imidazole curing agents, aromatic diamine curing agents, carboxylic acid curing agents, and the like can be used.
  • These curing agents, particularly imidazole-based curing agents include those that are liquid at room temperature and those that are solid at room temperature such as powder and fine particles. Which to use may be appropriately selected according to the application.
  • an acid anhydride that is liquid at normal temperature and a liquid imidazole curing agent are preferably used.
  • acid anhydrides that are liquid at room temperature include hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride.
  • imidazole curing agent include 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-ethyl-4-methylimidazole, and the like.
  • solid curing agents at room temperature examples include 2-methylimidazole, 2-phenylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid addition Such as things.
  • a curing agent that is liquid at room temperature has a fast onset of curing reaction and a high reaction rate, it is preferable to use a liquid curing agent when heat curing is subsequently performed after printing of the adhesive.
  • a liquid curing agent when heat curing is subsequently performed after printing of the adhesive.
  • the curing reaction hardly proceeds during storage.
  • the adhesive used for the transfer film it is preferable to use a powder or fine particle curing agent at room temperature.
  • the blending amount of the curing agent may be appropriately determined according to the epoxy equivalent of (C) the epoxy resin, but is preferably 0.8 to 1.2 equivalents, more preferably 1 equivalent to 1 equivalent of epoxy resin. 0.8 to 1.0 equivalent.
  • the inorganic filler is an inorganic filler having an average particle diameter of 1 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 100 nm or less.
  • the inorganic filler is preferable in that it can contribute not only to viscosity adjustment but also to improvement in bonding strength.
  • the average particle diameter means 50% particle diameter (D50), and a particle size distribution measuring device (Nikkiso Co., Ltd., Nanotrac (registered trademark) particle size distribution measuring device UPA-EX150) applying the laser Doppler method, etc. Can be measured.
  • a particle size distribution measuring device Nikkiso Co., Ltd., Nanotrac (registered trademark) particle size distribution measuring device UPA-EX150
  • anhydrous silica, aluminum hydroxide, talc, clay and the like can be used as the inorganic filler.
  • the filler is preferably 1 to 30% by mass of the resin content (total amount of acrylic resin and epoxy resin). If it exceeds 30% by mass, the viscosity becomes too high, and there is a possibility that the stringing or plate separation at the time of printing may be deteriorated. If it is less than 1% by mass, thixotropic properties cannot be imparted.
  • the filler content is preferably 3 to 30% by mass, more preferably 10 to 30% by mass.
  • the printing adhesive of this embodiment is obtained by dissolving the above components (A) to (D) in an organic solvent.
  • organic solvent ester organic solvents such as propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, and ⁇ -butyrolactone can be used.
  • the organic solvent is used from the viewpoint of viscosity adjustment, as will be described later, so that the adhesive can be applied to screen printing.
  • the amount of the solvent is selected so that the viscosity characteristic of the finally obtained adhesive satisfies the following range. That is, it is necessary to add such an amount that the viscosity is 15 to 800 Pa ⁇ s when the rotation speed is 1 rpm and the viscosity is 4 to 200 Pa ⁇ s when the rotation speed is 50 rpm.
  • the type of the solvent, the types of the components (A), (B), (C), and (D), the combination, and the like are appropriately selected.
  • the solvent amount is preferably 55% by weight or less of the total amount of the adhesive.
  • the printing type adhesive of this embodiment may contain the (F) antifoaming agent further as needed.
  • An antifoaming agent is preferable because it can defoam bubbles entrained during printing. In the case of screen printing, bubbles are easily involved when the adhesive is spread and pushed in as a squeegee. When it is cured while enclosing air bubbles, the cured product is in a state where air bubbles are included. Bubbles contained in the cured product may cause problems such as a decrease in bonding strength and heat resistance due to swelling at high temperatures. It is preferable to make it disappear.
  • the content of the antifoaming agent is preferably 0 to 2% by mass, more preferably 0 to 1% by mass, based on the total amount of the adhesive.
  • the printing type adhesive of this embodiment includes the above (A) acrylic resin, (B) epoxy resin, (C) curing agent, (D) inorganic filler, (E) solvent, and (F )
  • thermoplastic resins other than acrylic resins polyolefin resins, polyester resins, etc.
  • thermosetting resins other than epoxy resins for example, phenol resins, melamine resins, oxazine resins
  • a curing accelerator, a silane coupling agent, a leveling agent, a surfactant, a flame retardant, and the like are appropriately blended as long as the viscosity characteristics of the printing adhesive of the present embodiment are not impaired. Also good.
  • the printing type adhesive of the present invention comprises mixing the components (A) to (D) as described above, further mixing the components (F) and (G), which are added as necessary, and (E) a solvent. And mixing using a ball mill, a homogenizer or the like.
  • the mixing order is not particularly limited.
  • the printing type adhesive of the present embodiment has a viscosity of 15 to 800 Pa ⁇ s at a rotation speed of 1 rpm as measured with an E-type viscometer (100 to 800 Pa ⁇ s when a paint separation property is required) and a rotation speed of 50 rpm.
  • the viscosity is adjusted to 4 to 200 Pa ⁇ s (4 to 13 Pa ⁇ s when smoothness of the printing surface is required).
  • the viscosity at 50 rpm is less than 4 Pa ⁇ s, the printed adhesive tends to flow out, and when it exceeds 200 Pa ⁇ s, the separation of the plate is lowered and unevenness is likely to occur in the printed portion.
  • the printing surface when it is desired to be smooth, it is preferably set to 13 Pa ⁇ s or less. Further, when the pressure is less than 15 Pa ⁇ s at 1 rpm, the viscosity becomes too low, causing the adhesive to flow out of the printed portion and the like, making it difficult to apply a thick adhesive.
  • high-precision color separation such as a conductive portion and an adhesive portion is required, it is preferably 100 Pa ⁇ s or more. On the other hand, when it exceeds 800 Pa ⁇ s, the viscosity becomes too high, and it becomes difficult to apply the coating smoothly on the screen, and the printed portion is likely to be uneven.
  • the method for producing a joined body according to the present invention comprises a step of applying the printing adhesive of the present invention to the first adherend by screen printing and then heating at 100 to 250 ° C .; A step of placing two adherends; and a step of heating to 100 to 250 ° C. to thermally cure the adhesive application portion.
  • the manufacturing method of the joined body of the present invention is suitable when the first adherend is a flexible printed wiring board or a reinforcing board, and the second adherend is a reinforcing board or a flexible printed wiring board.
  • the first adherend is a flexible printed wiring board on which a conductive portion is printed
  • 3D to 30% by mass, preferably 10 to 30% of the (D) inorganic filler is used as the printing type adhesive.
  • a printing type adhesive containing mass% is used, and application printing is performed on the part where the conductive part is not printed with the printing type adhesive.
  • a method for producing a joined body wherein a transfer film obtained by applying and printing any one of the printing adhesives of the above-described embodiment on a release film by screen printing and a first film are provided.
  • a step of producing the transfer film by applying the printing adhesive by screen printing and then heating at 50 to 100 ° C. may be included.
  • the adhesive part preferably contains (D) the inorganic filler in an amount of 3 to 30% by mass of the resin content.
  • the adhesive can be printed on the adherend such as a flexible printed wiring board and a copper-clad laminate by screen printing only at a portion where the adhesive needs to be applied.
  • the printing type adhesive 12 of the present invention is placed on a silk screen 10 having openings 10a of a pattern to be bonded, and spread using a spatula such as a squeegee 11 (FIG. 2A). Then, the adhesive is pushed out from the opening 10a, and the adhesive pattern is applied to the adherend (flexible printed wiring board, copper-clad laminate, etc.) 13 (FIG. 2B).
  • 12 ' is the applied adhesive.
  • the viscosity when extending with a squeegee, the viscosity is such that it does not spread on the screen, and where a large shear stress that passes through the opening is generated, the viscosity Can be lowered and pass smoothly, and hence the separation of the plate is facilitated.
  • the amount of adhesive placed on the screen during printing is appropriately selected according to the printing amount. Therefore, when performing continuous printing, it is necessary to mount an amount necessary for continuous printing.
  • the adhesive pattern After the adhesive pattern is printed, heat at 100 to 250 ° C. for 1 minute to 1 hour. By heating, the solvent contained in the adhesive is volatilized to form a B stage. Further, the acrylic resin is softened and melted by heating, and can flow into the recesses of the adherend (flexible printed wiring board, reinforcing plate, etc.).
  • the other adherend (reinforcing plate) to be bonded is placed on the B-staged adhesive part and temporarily bonded at 60 to 160 ° C. using a laminator of 0.1 to 1 MPa.
  • the temporarily bonded portion is cured by heating at 100 to 250 ° C. for 30 minutes to 3 hours.
  • curing agent react and it thermosets and a joined body is obtained.
  • the adhesive can be applied to the part (pattern) to be bonded by screen printing, it is not necessary to cut out like the conventional film type adhesive, and is discarded. There is no part.
  • the portion (pattern) to be bonded is not limited to a macro portion that bonds a reinforcing plate in a flexible printed wiring board as shown in FIG.
  • an adhesive can be selectively printed on a portion 5 other than the conductive portion 4 in the flexible printed wiring board 1 ′ on which the conductive pattern 4 is printed.
  • the adhesive containing 3% by mass or more, preferably 10% by mass or more of the resin content of the inorganic filler, the width of 100 ⁇ m or more can be applied separately by distinguishing the adhesive application part and the non-application part. Since it is possible, even a micro pattern that requires such precise adjustment can be screen-printed.
  • the printing type adhesive is screen-printed on the first adherend, but the manufacturing method of the joined body using the printing type adhesive of the present invention is limited to this. Not. You may transfer an adhesive agent on a 1st to-be-adhered body using the film for transfer produced using the printing type adhesive agent of this invention. It is also possible to produce a joined body by placing the second adherend on the transferred adhesive and heating to 100 to 250 ° C. to thermally cure the transferred adhesive portion. it can.
  • the printing type adhesive of the present invention is not particularly limited, but is suitably used for joining a flexible printed wiring board, a copper-clad laminate and a reinforcing plate.
  • the position where the reinforcing plate is bonded to the flexible printed wiring board or the copper-clad laminate varies depending on the product, but according to the screen printing method, it is only necessary to prepare a silk screen corresponding to the pattern, and the film adhesive As in the case of using, cutting work for each film is not necessary, and further, there is no need to discard parts, which is economical.
  • the target flexible printed wiring board is a laminate (copper-clad laminate) of a plurality of insulating films and metal foils serving as base films, and a circuit is formed on one or both sides. In some cases, the circuit is further covered with an insulating film (so-called coverlay).
  • the base film examples include a polyimide film, a polyester film, a polyether ether ketone film, and a polyphenylene sulfide film.
  • a plastic film such as a polyimide film
  • a prepreg sheet based on a glass fiber reinforced resin sheet, a nonwoven fabric, or the like may be used.
  • the metal foil examples include copper foil and aluminum foil, and copper foil is preferably used.
  • a plastic film such as a polyimide film, a polyester film, a polyetheretherketone film, or a polyphenylene sulfide film is used.
  • Metal plates such as an aluminum board and a silicon steel plate
  • Plastic laminated boards such as a paper phenol laminated board and a glass epoxy laminated board
  • Plastic boards such as a polyimide board, a polypropylene board, a polyethylene board, etc. are used. It is done.
  • the present invention also includes the production of a transfer film for transferring the adhesive to the first adherend.
  • the transfer film can be produced by screen-printing the printing adhesive on a release film and then drying by heating.
  • the solvent is volatilized to a dry state by heating at 50 to 100 ° C., more preferably by heating at 50 to 100 ° C. for 0.5 to 2 hours.
  • a release film having a tape peeling force of less than 600 mN / 50 mm is usually used.
  • the transfer film may be a film on which a conductive portion and an adhesive portion are printed.
  • the transfer film on which the conductive part and the adhesive part are pattern-printed is printed on the release film using a conductive adhesive such as silver paste, and on the part where the conductive part is not printed, It is manufactured by printing and drying the printing type adhesive of the present invention. After printing the adhesive pattern, the conductive adhesive may be printed on a portion where the adhesive is not printed.
  • the release film is composed of the conductive part and the adhesive part corresponding to FIG. What is necessary is just to transfer to a 1st to-be-adhered body using the film for transfer on which the pattern was printed.
  • the release film on which the conductive pattern and the adhesive pattern are printed is overlapped with the first adherend as a transfer film and heated at 50 to 100 ° C., so that the conductive portion and the adhesive portion are attached to the first adherend. Can be transferred to.
  • an inorganic filler is used in an amount of 3 to 30% by weight, preferably 10 to 10% of the resin amount from the viewpoint of coating the conductive part and the adhesive part separately. It is preferable to use a printing type adhesive containing 30% by mass.
  • the curing agent (C) contained in the adhesive is a solid curing at room temperature so that the transfer film on which the adhesive part of a predetermined pattern is printed can be mass-produced and stored in advance. It is preferable to use an agent.
  • a joined body can be manufactured by placing the second adherend on the first adherend transferred using the transfer film, heating at 100 to 250 ° C., and thermosetting the adhesive portion. . Even in the adhesive portion transferred using the transfer film, it is possible to produce a bonded body having the same bonding strength and heat resistance as when the adhesive is applied and printed directly on the first adherend. .
  • the present invention also includes a transfer film produced using the printing adhesive of the present invention.
  • the epoxy resin contains (A) 30 to 70% by mass of the amount of the acrylic resin, (C) a curing agent, and (D) an inorganic filler having an average particle size of 1 ⁇ m or less.
  • (Appendix 2) A transfer film in which a conductive part and an adhesive part are printed on a release film, wherein the adhesive part (C) includes a solid curing agent, and the (D The transfer film according to supplementary note 1, wherein the inorganic filler is contained in an amount of 3 to 30% by mass, preferably 10 to 30% by mass of the resin content.
  • the flow-out amount of the printed part was measured with a microscope. As shown in FIG. 4, the flow-out amount was measured as the length (d) that protruded from the portion where the adhesive was to be applied (dotted line portion). Depending on the amount of protrusion (d), it is “excellent” when it is 0.05 mm or less, “good” when it is 0.05 to 0.1 mm, and “normal” when it is 0.1 to 0.2 mm. The case of exceeding 0.2 mm was defined as “defective”.
  • Threading The presence or absence of threading during screen printing was visually observed. The case where threading was observed was judged as “bad” and the case where threading was not observed was judged as “good”.
  • Thick film printability The thickness of the printed part was measured, and if it was 50 ⁇ m or more, it was judged as “good” and if it was less than 50 ⁇ m, it was judged as “bad”.
  • Printing adhesive No. having the composition shown in Table 1 and Table 2.
  • 1-6 and 11-16 were prepared.
  • Acrylic resin A1 Vanare resin GH-7190 (weight average molecular weight 120,000) manufactured by Shin-Nakamura Kogyo
  • Acrylic resin A2 Shin-Nakamura Vanade resin GH-7185 (weight average molecular weight 60,000)
  • Epoxy resin EPICLON-N740 from DIC (epoxy equivalent 180 g / eq)
  • Filler AEROSILRX300 (silica fine powder with a particle size of 7 nm) manufactured by Nippon Aerosil Co., Ltd.
  • Acid anhydride Rikacid MH-700 from Nippon Rika Co., Ltd. (It is a mixture of 4-methylhexahydrophthalic acid and methylhexahydrophthalic acid and is liquid at normal temperature) Imidazole: 2E4MZ from Shikoku Chemicals (2-ethyl-4-methylimidazole, which is liquid at room temperature) Antifoaming agent: BYK-54 from Big Chemie Japan
  • the unevenness of the printed portion can be reduced by reducing the viscosity at a high shear rate, even if the amount of the solvent is reduced, but the heat resistance cannot be satisfied ( No. 16).
  • the adhesive using the solvent E1 having a boiling point of less than 160 ° C. satisfies the continuous printability at both printing speeds of 10 mm / sec and 30 mm / sec, even if the viscosity characteristics are similar. I could't.
  • the adhesive using the solvent E2 having a boiling point of 218 ° C. was able to satisfy the continuous printability even at a printing speed of 30 mm / sec.
  • the heat resistance is too low (No. 23, 24). Conversely, if the epoxy resin content is too high relative to the acrylic resin, the bonding strength is low. When the blended amount of the epoxy resin exceeded 50 parts by mass of the blended amount of the acrylic resin, the product specification of 10 N / cm could not be satisfied (No. 21, 22).
  • Printing adhesive No. having the composition shown in Table 5 31-33 was prepared.
  • Sanmide LH210 trade name of Air Products
  • the continuous printability of the above evaluation method was evaluated, and (9) a transfer film was prepared based on the coatability, and the coatability was evaluated.
  • the printing-type adhesive No. prepared above was used. In the same manner as for No. 1, the coatability was evaluated.
  • a cover lay film (release film 38E0010GT (110 mN / 50 mm) manufactured by Fujimori Kogyo Co., Ltd.) was applied to the produced transfer film, and then heated at 60 ° C. for 48 hours. It was stored for 7 days in this state.
  • the cover lay film of the transfer film-like adhesive was peeled off and heated at 70 ° C. in a state of being bonded to the first adherend (reinforcing plate), and then the release film was peeled off.
  • a pattern composed of an Ag conductive portion and an adhesive portion could be transferred onto the first adherend.
  • a flexible printed wiring board is placed as the second adherend on the surface of the first adherend having the transferred conductive pattern and adhesive pattern, heated at 70 ° C., and then at 170 ° C. and 3 MPa for 30 minutes. Press-cured for a minute to obtain a joined body. About the obtained joined body, peeling strength and heat resistance were evaluated and measured based on the said evaluation method. The results are shown in Table 5.
  • the filler content is less than 3% by weight based on the resin content.
  • No. 1 since the viscosity was low, it was not possible to satisfy a high color separation property.
  • the 31-33 adhesive was able to satisfy a high level of paintability. Therefore, the printing type adhesive of the present invention can have a high level of paintability by adjusting the filler content. Further, even when applied to a transfer film, the joined body obtained by the transferred adhesive had a predetermined peel strength and was able to satisfy heat resistance.
  • composition No. Concavities and convexities were observed on the printed surface of the adhesive part of the transfer film produced using 31-33, but the surface of the transfer part obtained by transfer was a contact surface (smooth surface) with the release film. So it doesn't matter.
  • the printing type adhesive of the present invention can apply the adhesive to the necessary part of the adherend by screen printing, an economic effect can be obtained by applying it to the part where the film adhesive was used. It is done.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesive Tapes (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Combinations Of Printed Boards (AREA)

Abstract

La présente invention concerne un adhésif imprimable pouvant être imprimé par sérigraphie en un profil adhésif, qui présente en outre une résistance thermique et une force d'assemblage satisfaisantes. L'adhésif imprimable comprend (A) une résine acrylique ayant une masse moléculaire moyenne en poids (Mw) de 80 000 à 300 000, (B) de 30 à 70 % en poids d'une résine époxy relativement à la résine acrylique (A), (C) un durcissant, (D) une charge inorganique ayant un diamètre moyen de particules de 1 µm ou moins, et (E) un solvant. La viscosité, selon une mesure de viscosité de type E, est de 15 à 800 Pa∙s à une vitesse de révolution de 1 tr/min et de 4 à 200 Pa∙s à une vitesse de révolution de 50 tr/min.
PCT/JP2013/055905 2012-03-07 2013-03-05 Adhésif imprimable et procédé associé de fabrication d'un corps assemblé WO2013133240A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201380012877.6A CN104185667B (zh) 2012-03-07 2013-03-05 印刷型胶粘剂和使用该胶粘剂的接合体的制造方法
JP2014503848A JP6033841B2 (ja) 2012-03-07 2013-03-05 印刷型接着剤及びこれを用いた接合体の製造方法

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JP2012-050228 2012-03-07
JP2012050228 2012-03-07

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JP6940516B2 (ja) * 2016-11-18 2021-09-29 住友電気工業株式会社 接着剤組成物及びプリント配線板

Citations (3)

* Cited by examiner, † Cited by third party
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WO2003103352A1 (fr) * 2002-06-04 2003-12-11 住友電気工業株式会社 Carte pour cablage imprime, carte de cablage imprime et leur procede de fabrication
JP2009084336A (ja) * 2007-09-28 2009-04-23 Kimoto & Co Ltd 粘接着剤および粘接着シート
JP2011225856A (ja) * 2010-03-31 2011-11-10 Toray Ind Inc 電子機器用接着剤組成物およびそれを用いた電子機器用接着剤シート

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JP3980810B2 (ja) * 2000-04-07 2007-09-26 日立化成ポリマー株式会社 フレキシブルプリント配線板積層用接着剤組成物および接着フィルム
JP5008190B2 (ja) * 2007-06-15 2012-08-22 信越化学工業株式会社 スクリーン印刷用接着剤組成物
JP5485523B2 (ja) * 2008-08-19 2014-05-07 積水化学工業株式会社 スクリーン印刷用接着剤
JP4976481B2 (ja) * 2009-12-04 2012-07-18 日東電工株式会社 熱硬化型ダイボンドフィルム、ダイシング・ダイボンドフィルム、及び、半導体装置
KR20130041776A (ko) * 2010-03-31 2013-04-25 린텍 코포레이션 접착제 조성물, 접착 시트 및 반도체 장치의 제조 방법
CN102834907B (zh) * 2010-04-13 2016-03-16 积水化学工业株式会社 半导体芯片接合用粘接材料、半导体芯片接合用粘接膜、半导体装置的制造方法及半导体装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003103352A1 (fr) * 2002-06-04 2003-12-11 住友電気工業株式会社 Carte pour cablage imprime, carte de cablage imprime et leur procede de fabrication
JP2009084336A (ja) * 2007-09-28 2009-04-23 Kimoto & Co Ltd 粘接着剤および粘接着シート
JP2011225856A (ja) * 2010-03-31 2011-11-10 Toray Ind Inc 電子機器用接着剤組成物およびそれを用いた電子機器用接着剤シート

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CN104185667B (zh) 2016-05-11
JP6033841B2 (ja) 2016-11-30
JPWO2013133240A1 (ja) 2015-07-30

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