WO2005090509A1 - Composition adhesive thermique photovulcanisable de type film - Google Patents

Composition adhesive thermique photovulcanisable de type film Download PDF

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Publication number
WO2005090509A1
WO2005090509A1 PCT/JP2005/005442 JP2005005442W WO2005090509A1 WO 2005090509 A1 WO2005090509 A1 WO 2005090509A1 JP 2005005442 W JP2005005442 W JP 2005005442W WO 2005090509 A1 WO2005090509 A1 WO 2005090509A1
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WIPO (PCT)
Prior art keywords
film
meth
acrylate
adhesive
photocurable
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PCT/JP2005/005442
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English (en)
Japanese (ja)
Inventor
Masayuki Osada
Yoshihide Arai
Takashi Nemoto
Original Assignee
Three Bond Co., Ltd.
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Publication date
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Priority to JP2006519447A priority Critical patent/JPWO2005090509A1/ja
Publication of WO2005090509A1 publication Critical patent/WO2005090509A1/fr

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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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to an engineering plastic, a photocurable heat-sensitive film-like adhesive composition suitable for bonding sheets, films, and plates using the same, and in particular, is inexpensive and is diversified to various parts in the future.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the present invention relates to a film adhesive composition suitable for bonding a film or the like. Background art
  • the liquid adhesive can be adhered by directly applying it to the adherend, applying it, and pasting it together.It can be freely adhered to regardless of the shape and size of the adherend, so it can be used in various places. It is used.
  • screen printing and in-situ coating using a bar coater have problems in that the coating amount varies and the thickness becomes uneven.
  • the adhesive such as a so-called double-sided tape is obtained by impregnating a base material such as paper or nonwoven fabric with an acryl-based adhesive and protecting the adhesive surface with release paper.
  • the reactive pressure-sensitive adhesive mixes a component having a crosslinkable reactive group in addition to the adhesive component, and reacts the crosslinkable reactive group immediately before or after lamination with the adherend to three-dimensionally crosslink the composition.
  • the reactive pressure-sensitive adhesive mixes a component having a crosslinkable reactive group in addition to the adhesive component, and reacts the crosslinkable reactive group immediately before or after lamination with the adherend to three-dimensionally crosslink the composition.
  • JP-A-2003-186365 discloses a photoreaction comprising a compound having a crosslinkable reactive group such as an epoxy resin, a bullet compound, and an unsaturated polyurethane, and a cation or radical generating initiator.
  • Hot melt adhesive sheet is disclosed.
  • Japanese Patent Application Laid-Open No. 1-141969 discloses an ultraviolet-crosslinkable hot-melt adhesive composition comprising a hot-melt adhesive-based component, an ultraviolet-crosslinkable oligomer, and a photoinitiator. I have. Purpose of
  • hot-melt type reactive compositions basically attach importance to the initial tackiness, and most of them have tackiness at room temperature.
  • Hot-melt performance is used when coating in a sheet form. There are many things. In other words, it is used as a method of removing the solvent from what has been conventionally diluted and coated with a solvent, etc., and the coated material has adhesive properties and can be bonded only by pressing. It becomes. Such adhesives are irradiated with ultraviolet light The final adhesion when the cross-linkable reactive component was cured by the above method was insufficient, and the ability to adhere the hardly adherent adherend was not high.
  • having adhesiveness at room temperature has the advantage that temporary fixation and temporary lamination can be performed simply by pressure bonding, but it is necessary to protect the adhesive surface with release paper when not in use.
  • release paper is not required, and there is a disadvantage that waste is generated.
  • punching may be used, for example, when the adherend is to be formed into a desired shape after being adhered. At this time, if adhesiveness remains in the bonding adhesive, the adhesive will adhere to the punching blades, etc., causing the sharpness of the blades to become dull, reducing the processing accuracy due to burrs, etc. The frequency of washing was increased and workability was problematic.
  • tackifier U for imparting tackiness at normal temperature. Even in such cases, it cannot be used without release paper because it has some tackiness and tackiness at room temperature. It is conceivable that powder or the like may be adhered to the adhesive surface to reduce the stickiness of the surface.However, it is not possible to prevent sticking over a long period of time and the powder will hinder the adhesion during use. Not good. In addition, although the adhesiveness of the surface can be eliminated, the adhesiveness and tackiness remain inside, so that the workability of the above-mentioned punching process cannot be improved.
  • an object of the present invention is to provide an adherend that has no tackiness or tackiness at room temperature, melts when heated, develops tackiness, and hardens a crosslinkable component by irradiation with ultraviolet light. It is an object of the present invention to provide a film-like adhesive composition which can strongly adhere to a film. Disclosure of the invention
  • the present invention firstly provides at least one thermoplastic elastomer selected from (A) urethane (meth) acrylate, (B) a polyurethane elastomer, a polyester elastomer, and a polyamide elastomer.
  • the present invention relates to a photocurable heat-sensitive film-like adhesive composition comprising (C) a photoinitiator and (D) a thermoplastic polyester resin.
  • the present invention relates to a bonding method comprising sandwiching the above-mentioned film / film adhesive composition between adherends, heat-pressing, and then irradiating ultraviolet rays.
  • the urethane (meth) acrylate of the component (A) of the photocurable thermosensitive film adhesive composition of the present invention is a compound having a urethane bond in the molecule and having a (meth) acryloyl group in the molecule. is there.
  • (meth) acrylate is a generic term for acrylate and methacrylate. Preferred examples include those obtained by reacting a polyol compound with a polyisocyanate compound, and further reacting a hydroxyl group-containing (meth) acrylate.
  • polyol compounds include polyether diols, polyether polyols, polyester polyols, polyester polyols, polycarbonate diols, polycarbonate polyols, polybutadiene diols, polybutadiene polyols, acryl-based diols, acryl-based Polyols and the like.
  • the preferred molecular weight of these polyol compounds is from 200 to 7,000. One or more of these are selected.
  • polyether polyol is preferable, and as a specific example, Is a polyol compound or a diol compound having a bisphenol A skeleton in a molecule and having a hydroxyl group at a terminal or a side chain as described in Japanese Patent No. 2,568,421, and ethylene in a molecule.
  • examples thereof include polyol compounds and diol compounds having an oxide-propylene oxide structure.
  • polyisocyanate compound used as a raw material of the component (A) examples include aromatic, aliphatic, and alicyclic polyisocyanates. Specific examples include diphenylmethane diisocyanate (MD I), Tolylene diisocyanate (TDI), Xylene diisocyanate (XDI), Isophorone diisocyanate (IPDI), Naphthylene diisocyanate (NDI), Trizine diisocyanate (TPDI) Hexamethylene diisocyanate (HD I), dicyclohexyl methane diisocyanate (HMD I), trimethyl hexamethylene diisocyanate (TMH DI), 1,3-bis (isocyanate (Natomethyl) cyclohexane, 1,4-tetramethylene diisocyanate and the like.
  • MD I diphenylmethane diisocyanate
  • TDI Tolylene diisocyanate
  • XDI Xy
  • HD I hexamethylene diisocyanate
  • HMD I dihexyl hexyl methane diisocyanate
  • TMHD I trimethylhexamethylene diisocyanate
  • hydroxyl group-containing (meth) acrylate compound as a raw material of the component (A) include 2-hydroxyhexyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxypuccinole (meta).
  • alkyl (meth) acrylates having 2 to 20
  • a catalyst in order to promote the urethanization reaction.
  • the catalyst include triethylamine, benzyl / reethylamine, methyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium bromide, triphenylphosphane and organic titanium-based catalysts, and organic bismuth catalysts.
  • Catalysts, organotin catalysts, organozinc catalysts, and the like can be used, but organic titanium catalysts and organozinc catalysts are preferably used in view of reactivity and product characteristics.
  • bisphenol A disclosed in Japanese Patent Application Laid-open No. Hei 6-301206 may be added to an alcohol obtained by chain-extending bisphenol A with polyethylene glycol or the like.
  • Urethane (meth) acrylates to which is added, and (meth) acrylate-modified perfluoropolyether urethane prepolymers disclosed in JP-A-10-237392 are also usable.
  • the component (A) urethane (meth) acrylate is preferably liquid at room temperature (about 25 ° C), and if it is liquid, it can be used in any of the molecular weight states of monomer, oligomer, and polymer. can do.
  • the component (B) is composed of a polyurethane elastomer, a polyester elastomer, and a polymer. It is a thermoplastic elastomer selected from mid-type elastomers. Thermoplastic elastomers have a molecular structure consisting of a copolymer having a soft layer (soft segment) and a hard layer (hard segment), and have a property located between plastic and rubber. The soft layer is made of a thermoplastic elastomer. Develop a unique rubber elasticity. This characteristic indicates the required plasticity and fluidity of the thermoplastic resin at the molding temperature, and shows rubber-like physical properties at room temperature before or after molding.
  • Polyurethane-based elastomers are polyurethanes composed of long-chain polyols and short-chain polyols (low-molecular-weight dalicol) and diisocyanates.
  • a polymer chain composed of diisocyanate and short-chain polyols forms a hard segment, and a polymer chain composed of diisocyanates and long-chain polyols forms It becomes a soft segment, and various polymers can be made depending on the type and amount of diisocyanate and long and short chain polyols.
  • Examples include Rezamine P1045, P1098, and P2045 manufactured by Dainichi Seika Kogyo Co., Ltd., and milactran P26S RNAT and P395SRNAT manufactured by Nippon Milactran.
  • polyester-based elastomer examples include those in which an aromatic polyester is used as a hard segment and an amorphous polyether or an aliphatic polyester is used as a soft segment.
  • Specific examples include polybutylene terephthalate / polytetramethylene ether glycol block copolymer. More specifically, there may be mentioned Toyobo's Perprene S-1001, S-2001 and S-3001, Toray DuPont's Nittrel G 4047, 475, and the like.
  • polyamide-based elastomer examples include a hard segment of nylon and a soft segment of polyester or polyol. Specific examples include a nylon 12 / polytetramethylene glycol block copolymer.
  • thermoplastic elastomer copolymers may be used alone, or two or more of them may be used in combination. More specifically, manufactured by Ube Industries, Ltd. UBE- PAE 1 20 1, PAE 1 200, Fuji Kasei Kogyo Co.
  • the mixing ratio of the component (A) and the component (B) varies depending on the molecular weight of the component (A), but is usually selected in the range of 20 to 200 parts by weight of the component (A) per 100 parts by weight of the component (B). You. If the amount is less than 20 parts by weight, the adhesiveness after light irradiation is inferior. If the amount is more than 200 parts by weight, tackiness tends to be exhibited. More preferably, it is 30 to 150 parts by weight.
  • the component (C) is a photoinitiator, and as the photoopening agent, a conventionally known photopolymerization initiator can be used.
  • a photoinitiator for example, acetophenone, jetoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -12-morpholinopropane-11, benzoin, benzoinethinoether, benzodinethinoether, penzinoresimetinolecetanore, benzophenone
  • the Examples include, but are not limited to, benzyl, methinolevenezyl phonoremate, thiocyanate xanthone, and getinolethioxanthone.
  • the amount of component (C) is not particularly limited as long as it is an amount sufficient to polymerize the methacryloyl / group of component (A). It can be suitably adjusted depending on the type of the component (C) used and the desired cured physical properties, but it is usually selected in the range of 0.1 to 10% by weight of the whole of the components (A) to (D).
  • the component (D) is a thermoplastic polyester resin.
  • the “thermoplastic polyester resin” is a polyester obtained by a polycondensation reaction between an organic polycarboxylic acid (mainly dicarboxylic acid) component having no polyunsaturated unsaturated bond and a polyol (mainly diol) component. It is also called linear saturated polyester resin.
  • polyvalent carboxylic acid component terephthalic acid, isophthalic acid, phthalic anhydride, hexahydrophthalic acid, adipic acid, azelanic acid, sebacic acid, dodecandioic acid, dimer acid, trimellitic acid, ⁇ -force prolataton and the like are used.
  • the polyhydric alcohol components include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentinole glycol, polyethylene glycol, polytetramethylene glycol, Trimethylolpropane, pentaerythritol and the like are used.
  • component (D) examples include Pylon 500, 560, 630 manufactured by Toyobo, Elytel UE 3700, UE 3800 manufactured by Unitika, Arakid 7018, 7052 L manufactured by Arakawa Chemical Industries, and LP-033 manufactured by Nippon Gohsei. , KE-710 and the like.
  • the component (D) can be used from a crystalline one to an amorphous one, but a low melting point and low crystalline one is more preferable.
  • the preferable properties of the component (D) include the Tg of the component (D).
  • the hardness is preferably 40 ° C to 35 ° C, the hardness at 25 ° C is 5 to 40 in Shore D, and the elongation at break is more than 800% to 3000%.
  • the Shore D hardness is JIS-K-62
  • the method specified in 53 and the elongation at break shall be measured by the method specified in JI SK-6251.
  • the added amount of the component (D) is preferably from 5 to 30% by weight of the entire components (A) to (D). 5 weight. / 0 less and hot melt production and tacky during heating is lower than, tends to decrease the adhesion during UV crosslinking with More than 30 wt% Yo.
  • Photocurable heat-sensitive film-like adhesive composition of the present invention [This can further contain other components. One of them is a vinyl monomer other than the component (A).
  • N-vinylpyrrolidone N-butylcaprolactam
  • vinylimidazole butylpyridine
  • isovol (meth) atalylate bornyl (meth) atalylate
  • tricyclodecal (meth) atalylate dicyclo Pentanyl (meth) acrylate, dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, atariloyl morpholine
  • 2- Hydroxyethyl (meth) acrylate 2-hydroxypropinole (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isop Pill (meta) acrylate, butyl (meth)
  • the following resins may be used in combination.
  • epoxy resin epoxy resin, phenol resin, silicone resin, urethane resin, acrylic resin, polyimide resin, phenoxy resin, polyvinyl butyral resin, polyacetal resin, polystyrene resin, polyethylene resin, polyisobutylene resin, alkyne / refenolene resin, and polycarbonate Net resin, polyester resin, acrylic rubber, melamine resin, and its modified resins.
  • resins, rubbers, and the like having a functional group having a polar group such as a hydroxyl group, a carboxyl group, a glycidyl group, a vinyl group, an amino group, etc. It is necessary to mix them in such an amount that tack does not appear at room temperature.
  • fillers such as tanolek, mai power, mica, calcium carbonate, titanium oxide silica powder, leveling agents, defoamers, lubricants, antistatic agents, ion adsorbents, wetting agents, dispersants, cups Ring agents, surface conditioners, and additives can also be used.
  • silane power examples include vinyltriethoxysilane, vinylinoletris-methoxyethoxy) silane, y-metaryloxypropyltrimethoxysilane, vinyltriacetoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane , 1- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -chloropropylpropylmethoxysilane, butyltrichlorosilane, ⁇ / —mercaptopropyltrimethoxysilane, ⁇ / aminopropyltriethoxysilane,] —] 3 aminoethyl) _ gamma one such chromatography ⁇ amino Pro built Increment Tokishishiran can be used alone or in combination of two or more.
  • the film adhesive of the present invention can be produced by dissolving or dispersing the above-mentioned components in an organic solvent, coating, and then volatilizing the organic solvent.
  • organic solvent include, but are not limited to, ester-based, ketone-based, ether-ester-based, chlorine-based, alcohol-based, ether-based, and hydrocarbon-based solvents.
  • a low-boiling solvent can be selected for use in coating and the like, and a high-boiling solvent can be selected for screen printing.
  • Film-like adhesive of the present invention is usually dryness 1 ⁇ 1 0 0 ⁇ ⁇ , is applied preferably to a thickness of 2 to 5 0 mu m.
  • the film adhesive of the present invention is usually coated and peeled off after drying to form a self-supporting film unit, but it is too thin, such as less than 1 / m, and is handled as a unit If it is difficult to do so, it may be stored in a state where it is attached to release paper or the like, and the release paper may be peeled off when used. However, since release paper becomes unnecessary after use and wastes, it is preferable not to use it as much as possible. It is also possible to form a film adhesive layer by coating on one adherend.
  • the film adhesive of the present invention has no tackiness at room temperature (about 25 ° C) and is flexible, so that it feels like a plastic film when touched with a finger. .
  • the film thickness is 1 ⁇ m or more, a form without using a release paper or a base material is also possible, and a product form in which only the film adhesive of the present invention is wound into a roll can be obtained.
  • a form using release paper may be used if desired.
  • the film adhesive of the present invention is sandwiched between the adherends, and the adherends are heated and pressed.
  • the heat compression bonding conditions vary depending on the composition of the composition and the melting temperature of the composition, which depends on the amount of the composition, but are usually in the range of 50 to 120 ° C and 0.1 to 0.5 ° C. Pressure conditions in the range of MPa are used. '
  • the film adhesive composition of the present invention is three-dimensionally cross-linked by ultraviolet irradiation to exhibit strong adhesiveness.
  • the irradiation condition of the ultraviolet ray can be selected according to the ordinary photocuring method.
  • Preferred irradiation amount of the ultraviolet is 1 ⁇ 3 j Z cm 2.
  • Examples of the light source for ultraviolet irradiation include a metal halide lamp and a high-pressure mercury lamp.
  • the adherend is irradiated with ultraviolet rays, and therefore, the adherend is preferably an ultraviolet-transparent one.
  • the adherend is not permeable to ultraviolet bran, it can be adhered by irradiating light immediately before lamination and thermocompression bonding immediately.However, a non-adhesive film may be formed on the film surface. It is lower than the former. Therefore, it is preferable to perform the ultraviolet irradiation after the thermocompression bonding.
  • the photocurable thermosensitive film-like adhesive composition of the present invention can be formed into a film. Since it does not have tackiness or tackiness at room temperature, it can be made into a form that does not require release paper, and it can be handled as a single film. Not only that, it is also advantageous when cutting films. In addition, it can be melted by thermocompression bonding to exhibit tackiness and adhere to an adherend. Furthermore, excellent adhesiveness is exhibited by light irradiation, and the adhesiveness does not decrease even when used in a high-temperature location.
  • Such properties of the photocurable heat-sensitive film-like adhesive composition of the present invention can be applied to engineering plastics, especially polyethylene terephthalate films and polycarbonate films, which are inexpensive and are expected to be diverted to various parts in the future.
  • it is particularly remarkable in the adhesion when one of these films is a polyether phthalate film, a polyether sanolephone film, or the like, which is expensive but is more reliable than the above films. It has a great effect.
  • the film adhesive of the present invention has high adhesion reliability not found in pressure-sensitive adhesives, improves heat resistance in particular, has a shrinkage rate not found in liquid adhesives, and particularly adherends in surface adhesion. This is useful for resolving warpage.
  • Synthesis Example 1 Polyetherdiol (EM53, manufactured by Asahi Denka Co., Ltd.) 2.0 moles of hexamethylene diisocyanate (HDI) in 1.9 moles, and butyl hydroxy toluene (BHT polyetherdiol) as a polymerization inhibitor 0 relative to the total weight of the mixture of HDI and.
  • E53 hexamethylene diisocyanate
  • BHT polyetherdiol butyl hydroxy toluene
  • Synthesis Example 2 Polyesterdiol (F15-20, manufactured by Asahi Denka) 4.0 moles of hexamethylene diisocyanate (HDI) and butylhydroxytoluene (BHT polyesterdiol) as a polymerization inhibitor 0.4% by weight based on the total weight of the mixture of phenol and HDI) and ethyl ethyl methine ketone (20% by weight based on the total weight of the mixture of polyester diol and HDI) as a diluent.
  • HDI hexamethylene diisocyanate
  • BHT polyesterdiol butylhydroxytoluene
  • the mixture was mixed in the presence thereof, added with 0.1% by weight of octyl zinc as a catalyst and reacted at 80 at room temperature for 2 hours to obtain a prepolymer having an isocyanate group at the terminal. Then, 4.0 mol of 2-hydroxyatalylate (2-HEA) was added to the mixture, and the mixture was stirred at 80 ° C. for 2 hours to obtain a urethane having an atariloyl group at the terminal.
  • 2-HEA 2-hydroxyatalylate
  • Synthesis Example 3 Polycarbonate diol (L-5651 manufactured by Asahi Kasei Corporation) 3.0 moles of hexamethylene diisocyanate (HDI) 4.0 moles of butylhydroxytoluene (BHT polycarbonate) as a polymerization inhibitor 0.4% by weight based on the total weight of the mixture of diol and HDI) and ethynolemethylketone as a diluent (20% by weight based on the total weight of the mixture of polycarbonate diol and HDI) Then, 0.1% by weight of octyl zinc was added as a catalyst to the mixture, and the mixture was reacted at 80 ° C. for 2 hours to give an iso-terminal.
  • HDI hexamethylene diisocyanate
  • BHT polycarbonate butylhydroxytoluene
  • An adhesive was prepared according to the formulation shown in Table 1.
  • UE820 (Dainippon Ink) is epoxy acrylate
  • EFN113HPX Showa High Polymer
  • Clayton FG (Clayton polymer) is styrene-based heat.
  • AR51 (Nippon Zeon) is a phthalyl elastomer
  • UE760 is a copolymer of ethylene vinyl acetate (Tosoichi)
  • V AGH Union Carbide
  • Preparation of film adhesive Various compositions obtained were coated on a PET film using a bar coater, dried at 1 ° C for 20 minutes and dried to a dry film thickness of 20 to 25 ⁇ . A film adhesive was obtained.
  • Adhesion 'Confirmation of tackiness The obtained films were overlapped at 25 ° C. and pressed with 0. IMP a to determine whether or not the film adhesive was fused. If the film surfaces are smooth and glossy when the films are peeled off, then ⁇ is determined.If the surface has no fine irregularities or has no gloss, the film is judged to have been peeled off by fusing the film. It was decided.
  • the obtained film-like adhesive was applied to PET (polyethylene terephthalate) film (75; am thickness), PC (polycarbonate) film (200 m thickness), PES (polyether sal Fon) (200 ⁇ m thick) Film, PEN (polyethylene naphthalate) ( ⁇ ⁇ ⁇ ⁇ thickness) Inserted between finolems and heated with a heat laminator (manufactured by MCK) at a heat roll temperature of 120 ° C and a passing speed of 0 Thermocompression bonding was performed for 5 MZ.
  • PET polyethylene terephthalate
  • PC polycarbonate
  • PES polyether sal Fon
  • PEN polyethylene naphthalate
  • UV irradiation was performed using a conveyor type UV irradiation machine under the condition of 300 000 mj / cm-2 to obtain a test piece.
  • the T-peel strength of the obtained test piece was measured with a tensile strength tester (Tensilon) at a tensile speed of 50 mmZ.
  • the obtained film adhesive is sandwiched between transparent PC plates (2 mm thick), and heated with a heat laminator (manufactured by MCK) at a temperature of 120 ° C and a passage speed of 0. Thermocompression bonding was performed for 5 M min. Thereafter, UV irradiation was performed using a conveyor-type UV irradiation machine under the condition of 300 OmjZcm-2 to obtain a test piece. The shear strength of the obtained test piece was measured by a tensile strength tester (Tensilon) at a tensile speed of 5 OmmZ.
  • a tensile strength tester Teensilon
  • 80 ° C creep test A PET film specimen was prepared under the same conditions as those used for the peel adhesion test, cut to a width of 10 mm, marked on the edge of the adhesive, and loaded with 50 g ( It was left for 12 h in an atmosphere of 80 ° C under a load of 5 g per lmm of adhesive width, and the state after the standing was observed. The separation distance from the initial marking was measured, and the one that fell was marked as X. The unit is mm. The results are also shown in Table 1. table 1
  • Pandex T-5205 (Dainippon Ink) 100 100 100 100 100 100 100 100 Thermoplastic raw gill
  • Lucilin TPO (BASF) 1 Polyestenol Pylon 500 (Toyobo) 20 30 40 50 90 60 (D) Arakido 7018 (Arakawa Chemical) 105 30 50 65
  • Pandex T-I 5205 (Dainippon Ink) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Thermoplastic Elastanolene S-1001 (Toyobo) 100 100
  • thermocurable thermosensitive film-like adhesive composition of the present invention is suitable for bonding plastic films, it can be used for applications such as bonding of membrane switches and touch panels, and bonding of display devices.

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

Abstract

Il est prévu un adhésif de type film ne présentant pas de propriétés d’adhésivité ou de collage à la température ambiante et que l’on peut donc manipuler comme film, tout en adhérant à un objet après chauffage et fusion, avec une bonne adhérence à l’objet après irradiation à la lumière. Un tel adhésif de type film peut s’obtenir en formant (A) un (méth)acrylate uréthane, (B) au moins un ou plusieurs élastomères thermoplastiques sélectionnés parmi les élastomères de polyuréthane, les élastomères de polyester et les élastomères de polyamide, (C) un photoinitiateur et (D) une résine polyester thermoplastique en forme de film.
PCT/JP2005/005442 2004-03-19 2005-03-17 Composition adhesive thermique photovulcanisable de type film WO2005090509A1 (fr)

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JP2007176108A (ja) * 2005-12-28 2007-07-12 Sharp Corp 電子機器のキャビネットをインサート成形する方法及び皮革製カバーによって覆われたキャビネットを有する電子機器
JP2008202020A (ja) * 2007-01-23 2008-09-04 Hitachi Chem Co Ltd 接着剤組成物、回路接続構造体及び半導体装置
JP2010090204A (ja) * 2008-10-04 2010-04-22 Three Bond Co Ltd 光硬化性接着剤組成物
WO2010084722A1 (fr) * 2009-01-26 2010-07-29 タツタ システム・エレクトロニクス株式会社 Composition adhésive
JP2014189723A (ja) * 2013-03-28 2014-10-06 Hitachi Chemical Co Ltd 画像表示装置用粘着性樹脂組成物、画像表示装置用粘着シート、画像表示装置の製造方法及び画像表示装置
KR101459124B1 (ko) * 2011-12-07 2014-11-07 제일모직주식회사 광경화형 점착제 조성물 및 이를 포함하는 디스플레이 장치
EP2770000A4 (fr) * 2011-10-19 2015-06-24 Dainippon Ink & Chemicals Composition de résine durcissable sous l'effet d'un rayonnement d'énergie active, adhésif et film stratifié
JP2015520787A (ja) * 2012-05-22 2015-07-23 ヘンケル ユーエス アイピー エルエルシー 光学的に透明な光硬化性液状接着剤
US9175196B2 (en) 2011-12-07 2015-11-03 Cheil Industries, Inc. Photocurable adhesive composition and display device comprising same
JP2017206579A (ja) * 2016-05-16 2017-11-24 東亞合成株式会社 プラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物
CN109134822A (zh) * 2018-07-24 2019-01-04 大连中海达科技有限公司 一种可紫外光交联的热塑性聚氨酯弹性体的合成方法
US10703942B2 (en) 2014-03-05 2020-07-07 Lumina Adhesives Ab Low cytotoxicity switchable adhesive compositions, medical dressings and skin coverings, and methods of treatment using same

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JP3108138B2 (ja) * 1991-07-30 2000-11-13 サンスター技研株式会社 紫外線架橋型ホットメルト組成物
JPH11256120A (ja) * 1997-10-29 1999-09-21 Ciba Specialty Chem Holding Inc 接着剤組成物
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007176108A (ja) * 2005-12-28 2007-07-12 Sharp Corp 電子機器のキャビネットをインサート成形する方法及び皮革製カバーによって覆われたキャビネットを有する電子機器
JP2008202020A (ja) * 2007-01-23 2008-09-04 Hitachi Chem Co Ltd 接着剤組成物、回路接続構造体及び半導体装置
KR20110066156A (ko) * 2008-10-04 2011-06-16 가부시끼가이샤 쓰리본드 광경화성 접착제 조성물
JP2010090204A (ja) * 2008-10-04 2010-04-22 Three Bond Co Ltd 光硬化性接着剤組成物
US9790405B2 (en) 2008-10-04 2017-10-17 Threebond Fine Chemical Co., Ltd. Photocurable adhesive composition
KR101667777B1 (ko) 2008-10-04 2016-10-19 쓰리본드 화인 케미칼 가부시키가이샤 광경화성 접착제 조성물
JP2010168510A (ja) * 2009-01-26 2010-08-05 Tatsuta System Electronics Kk 接着剤組成物
JP4580021B2 (ja) * 2009-01-26 2010-11-10 タツタ電線株式会社 接着剤組成物
WO2010084722A1 (fr) * 2009-01-26 2010-07-29 タツタ システム・エレクトロニクス株式会社 Composition adhésive
EP2770000A4 (fr) * 2011-10-19 2015-06-24 Dainippon Ink & Chemicals Composition de résine durcissable sous l'effet d'un rayonnement d'énergie active, adhésif et film stratifié
KR101459124B1 (ko) * 2011-12-07 2014-11-07 제일모직주식회사 광경화형 점착제 조성물 및 이를 포함하는 디스플레이 장치
US9175196B2 (en) 2011-12-07 2015-11-03 Cheil Industries, Inc. Photocurable adhesive composition and display device comprising same
JP2015520787A (ja) * 2012-05-22 2015-07-23 ヘンケル ユーエス アイピー エルエルシー 光学的に透明な光硬化性液状接着剤
JP2014189723A (ja) * 2013-03-28 2014-10-06 Hitachi Chemical Co Ltd 画像表示装置用粘着性樹脂組成物、画像表示装置用粘着シート、画像表示装置の製造方法及び画像表示装置
US10703942B2 (en) 2014-03-05 2020-07-07 Lumina Adhesives Ab Low cytotoxicity switchable adhesive compositions, medical dressings and skin coverings, and methods of treatment using same
JP2017206579A (ja) * 2016-05-16 2017-11-24 東亞合成株式会社 プラスチック製フィルム又はシート用活性エネルギー線硬化型接着剤組成物
CN109134822A (zh) * 2018-07-24 2019-01-04 大连中海达科技有限公司 一种可紫外光交联的热塑性聚氨酯弹性体的合成方法

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