WO2022003602A1 - A polyurethane adhesive composition, a polyurethane adhesive, a polyurethane adhesive tape, and the method for preparing the polyurethane adhesive tape - Google Patents

A polyurethane adhesive composition, a polyurethane adhesive, a polyurethane adhesive tape, and the method for preparing the polyurethane adhesive tape Download PDF

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Publication number
WO2022003602A1
WO2022003602A1 PCT/IB2021/055879 IB2021055879W WO2022003602A1 WO 2022003602 A1 WO2022003602 A1 WO 2022003602A1 IB 2021055879 W IB2021055879 W IB 2021055879W WO 2022003602 A1 WO2022003602 A1 WO 2022003602A1
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Prior art keywords
polyurethane adhesive
adhesive composition
weight
substrate
polyester diol
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PCT/IB2021/055879
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French (fr)
Inventor
Xue-Ha CHEN
Guannan YIN
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3M Innovative Properties Co
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3M Innovative Properties Co
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Publication of WO2022003602A1 publication Critical patent/WO2022003602A1/en
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    • 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
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2475/00—Presence of polyurethane
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Definitions

  • the present invention relates to the field of adhesives, in particular to a polyurethane adhesive composition, a polyurethane adhesive, an adhesive tape including the polyurethane adhesive, and a method for preparing the adhesive tape.
  • a protective film to protect a chip.
  • a protective film is needed to protect a chi.
  • a protective film is also needed to protect a chip from 200°C or higher temperature (even more than 260°C) for several minutes to dozens of minutes. Therefore, it is necessary to provide a protective film with good adhesion performance at room temperature and high-temperature resistance to meet this demand.
  • the deposition of high-performance coatings can be used to improve the optical properties of glass screens in the display manufacturing process.
  • a protective film is needed to protect regions on a glass screen where coatings are not needed to be coated.
  • this protective film must have good adhesion performance with a substrate, so as to avoid blistering, warping and falling off.
  • the protective film after the vapor deposition process, the protective film must be easily removed without leaving residual adhesives on the substrate. Therefore, it is necessary to provide a protective film with good adhesion performance at room temperature and high-temperature resistance to meet this demand.
  • One purpose of the present invention is to provide a polyurethane adhesive composition and a polyurethane adhesive based on the composition.
  • the polyurethane adhesive at least has good room-temperature adhesion performance and high-temperature resistance, so it can be used to solve some problems in the process of manufacturing chips or display glass screens.
  • Another purpose of the present invention is to provide a polyurethane adhesive tape.
  • Another purpose of the present invention is to provide a method for preparing a polyurethane adhesive tape.
  • the present invention provides a polyurethane adhesive composition, including: a) a polydiol, at least including a polyester diol having a weight average molecular weight of 400-4000; b) an aliphatic polycaprolactone triol having a weight average molecular weight of 100-600; and c) a polydiisocyanate, at least including one of a hexamethylene diisocyanate trimer and an isophorone diisocyanate trimer.
  • the polyester diol at least includes one of an aromatic polyester diol and a fatty acid based polyester diol.
  • the polyester diol has a weight average molecular weight of 500-3000.
  • the aliphatic polycaprolactone triol has a weight average molecular weight of 200-400.
  • the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01-1:0.7, preferably 1:0.04-1:0.5, particularly preferably 1:0.06-1:0.3.
  • the polydiol further includes a dimer diol.
  • the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1 : 1.
  • the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1 :0.04-l :0.3, and the weight ratio of the polyester diol to the dimer diol is 1:0.1-1: 1; preferably, the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.06-1:0.3, and the weight ratio of the polyester diol to the dimer diol is 1:0.1-1: 1.
  • the polyurethane adhesive composition further includes d) silica particles.
  • the average particle size (D50) of the silica particles is 5-15 pm, preferably 6-10 pm.
  • the silica particles at least include one of polydimethylsiloxane (PDMS) surface-modified silica particles, wax surface -modified silica particles, and surface-unmodified silica particles.
  • PDMS polydimethylsiloxane
  • the ratio of the weight of the silica particles to the total weight of the polydiol, aliphatic polycaprolactone triol and polydiisocyanate is 1.0: 100-5.1: 100.
  • the present invention provides a polyurethane adhesive, including a cured product of the polyurethane adhesive composition provided by the present invention.
  • the present invention provides an adhesive tape, including a substrate and the polyurethane adhesive provided by the present invention disposed on the substrate.
  • the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, release paper, or a release film.
  • the present invention provides a method for preparing a polyurethane adhesive tape, including the following steps: disposing the polyurethane adhesive composition provided by the present invention on a substrate; and curing the polyurethane adhesive composition.
  • Good room-temperature adhesion performance used herein refers to that a polyurethane adhesive or polyurethane adhesive tape can be adhered to a surface of a substrate (including but not limited to a glass substrate, a stainless steel substrate, or a silicon wafer substrate) at room temperature (23°C), and has good room-temperature 180° peeling force on the substrate.
  • “Good high-temperature resistance” used herein refers to that after a high-temperature process, a polyurethane adhesive or a polyurethane adhesive tape can still be adhered to the substrate without blistering and falling off, and can be completely removed from the surface of the protected substrate without leaving residual adhesives.
  • “Average particle size” used herein refers to the particle size of particles whose cumulative frequency (G or R) of particle size distribution is equal to 50%, also called as median diameter, also known as D50.
  • a polyurethane adhesive composition provided by the present invention includes: a) a polydiol, at least including a polyester diol having a weight average molecular weight of 400-4000; b) an aliphatic polycaprolactone triol having a weight average molecular weight of 100-600; and c) a polydiisocyanate, at least including one of a hexamethylene diisocyanate trimer and an isophorone diisocyanate trimer.
  • the polyester diol refers to a polyester polyol with a hydroxyl functionality of 2 obtained through condensation reaction of a dicarboxylic acid, a diol, and the like.
  • the polyester diol has a molecular weight of 400-4000, preferably 500-3000.
  • the polyester diol can adjust the polarity and cohesive strength of the polyurethane adhesive, so as to adjust the room-temperature adhesion performance and high-temperature resistance of the polyurethane adhesive.
  • the polyester diol may be a fatty acid based polyester diol.
  • the fatty acid based polyester diol may be Priplast 3162, Priplast 3172, Priplast 3192, or Priplast 3190 purchased from Croda Chemical (Shanghai) Co., Ltd. located in Shanghai, China.
  • the polyester diol may also be an aromatic polyester diol.
  • the aromatic polyester diol maybe X CPA-110 orXCPA-195 purchased from of Xuchuan Chemical (Suzhou) Co., Ltd. located in Suzhou, China.
  • the polydiol may further include a dimer diol.
  • the dimer diol may be prepared through hydrogenation reduction of dimer acid.
  • the dimer acid may be a complex mixture consisting of Cl 8 unsaturated fatty acid dimers with different structures and higher oligomers.
  • the dimer diol can adjust the polarity and cohesive strength of the polyurethane adhesive, so as to adjust the room-temperature adhesion performance and high-temperature resistance of the polyurethane adhesive.
  • the dimer diol may be Pripol 2033 or Pripol 2030 purchased from Croda Chemical (Shanghai) Co., Ltd. located in Shanghai, China.
  • the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1 : 1.
  • the polyurethane adhesive can have good high-temperature resistance.
  • the aliphatic polycaprolactone triol refers to a polyester polyol with a hydroxyl functionality of 3 formed through ring -opening polymerization of caprolactone, and the aliphatic polycaprolactone triol has a weight average molecular weight of 100-600, preferably 200-400.
  • the aliphatic polycaprolactone triol can increase the cross-linking degree of the polyurethane adhesive, thereby improving the high-temperature resistance of the polyurethane adhesive.
  • the aliphatic polycaprolactone triol may be Capa 3050 or Capa 3031 purchased from Perstorp UK Ltd. located in Cheshire, UK.
  • the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01-1:0.7, preferably 1:0.04-1:0.5.
  • the polyurethane adhesive can have good high-temperature resistance.
  • the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1 :0.01-1 :0.7, preferably 1 :0.04-l :0.5, and the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1 : 1.
  • the polyurethane adhesive can have good high-temperature resistance.
  • the polydiisocyanate at least includes one of a hexamethylene diisocyanate trimer and an isophorone diisocyanate trimer. The hexamethylene diisocyanate trimer and isophorone diisocyanate trimer can provide good room-temperature adhesion performance and high-temperature resistance for the polyurethane adhesive.
  • the hexamethylene diisocyanate trimer may be N3800, N3390 or N3300 purchased from Covestro located in Shanghai, China.
  • the isophorone diisocyanate trimer may be Z4470 purchased from Covestro located in Shanghai, China.
  • the polyurethane adhesive composition provided by the present invention may further include silica particles.
  • the average particle size D50 of the silica particles is 5-15 pm, preferably 6-10 pm.
  • the silica particles can adjust the room-temperature adhesion performance of the polyurethane adhesive and improve the high-temperature resistance of the polyurethane adhesive.
  • the silica particles may be one or more selected from the group consisting of polydimethylsiloxane (PDMS) surface -modified silica particles, wax surface-modified silica particles, and surface-unmodified silica particles.
  • PDMS polydimethylsiloxane
  • the polydimethylsiloxane (PDMS) surface-modified silica particles may be Acematt 3300 purchased from Evonik located in Shanghai, China.
  • the wax surface -modified silica particles may be OK520 purchased from Evonik located in Shanghai, China.
  • the surface-unmodified silica particles may be TS-100 purchased from Evonik located in Shanghai, China.
  • the ratio of the weight of the silica particles to the total weight of the polydiol, aliphatic polycaprolactone triol and polydiisocyanate is 1.0:100-5.1:100.
  • the ratio (A/B) may be calculated according to the following formula:
  • A weight of silica particles
  • A/B (weight of silica particles) / (weight of polydiol + weight of aliphatic polycaprolactone triol + weight of polydiisocyanate).
  • the weight of the polydiol, the weight of the aliphatic polycaprolactone triol and the weight of the polydiisocyanate may be respectively calculated according to the following formulas:
  • Weight of polydiol weight of polydiol solution c solid content of polydiol solution
  • Weight of aliphatic polycaprolactone triol weight of aliphatic polycaprolactone triol solution c solid content of aliphatic polycaprolactone triol solution
  • Weight of polydiisocyanate weight of polydiisocyanate solution c solid content of polydiisocyanate solution.
  • a polyurethane adhesive provided by the present invention includes a cured product of the polyurethane adhesive composition provided by the present invention.
  • the polyurethane adhesive may be prepared according to the following steps: step 1 : adding all component of the polyurethane adhesive composition into a suitable container for mixing at room temperature; step 2: putting the all mixed components of the polyurethane adhesive composition into an oven for reaction and curing to obtain a polyurethane adhesive.
  • step 2 after the mixed components of the polyurethane adhesive composition are put into the oven, the temperature is increased from 120°C to 150°C and kept for 20 min to enable the polyurethane adhesive composition to react and be cured to obtain the polyurethane adhesive.
  • step 2 after the mixed components of the polyurethane adhesive composition are put into the oven, the temperature may be increased from 120°C to 150°C and kept for 20 min, and then the temperature may be decreased to 80°C and kept for 24h to complete the curing reaction.
  • step 1 all components of the polyurethane adhesive composition except silica particles may be first added into a suitable container, and then the silica particles may be added into the container and dispersed at high speed of 2500 rpm for 5-15 min.
  • the polyurethane adhesive may be stored at room temperature.
  • the polyurethane adhesive provided by the present invention at least has good room-temperature adhesion performance and good high-temperature resistance.
  • the polyurethane adhesive composition provided by the present invention includes an appropriate amount of polydiol, aliphatic polycaprolactone triol and polydiisocyanate
  • the polyurethane adhesive prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a glass substrate.
  • the polyurethane adhesive prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a silicon wafer substrate.
  • the polyurethane adhesive prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a stainless steel substrate.
  • An adhesive tape also called “protective film” provided by the present invention includes a substrate and a polyurethane adhesive provided by the present invention disposed on the substrate.
  • the polyurethane adhesive is detailed in the “Polyurethane adhesive” in this description, and thus will not be repetitively described here.
  • the polyurethane adhesive may be provided on at least one side of the substrate.
  • the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, release paper, or a release fdm.
  • the polyurethane adhesive provided by the present invention at least has good room-temperature adhesion performance and good high-temperature resistance.
  • the polyurethane adhesive tape prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a glass substrate.
  • the polyurethane adhesive tape prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a silicon wafer substrate.
  • the polyurethane adhesive tape prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a stainless steel substrate.
  • a method for preparing a polyurethane adhesive tape provided by the present invention includes the following steps: disposing the polyurethane adhesive composition provided by the present invention on a substrate; and curing the polyurethane adhesive composition.
  • Components of the polyurethane adhesive composition are detailed in the “Polyurethane adhesive composition” in this description, and thus will not be repetitively described here.
  • the preparation method may comprise the following steps: step 1 : adding all component of the polyurethane adhesive composition into a suitable container for mixing at room temperature; step 2: coating the mixed polyurethane adhesive composition on a surface of a substrate; and step 3 : putting the substrate coated with the polyurethane adhesive composition into an oven for reaction and curing to obtain a polyurethane adhesive.
  • step 3 after the substrate coated with the polyurethane adhesive composition is put into the oven, the temperature is increased from 120°C to 150°C and kept for 20 min to enable the polyurethane adhesive composition to react and be cured to obtain the polyurethane adhesive.
  • step 3 after the substrate coated with the polyurethane adhesive composition is put into the oven, the temperature may be increased from 120°C to 150°C and kept for 20 min, and then the temperature may be decreased to 80°C and kept for 24h to complete the curing reaction.
  • step 1 all components of the polyurethane adhesive composition except silica particles may be first added into a suitable container, and then the silica particles may be added into the container and dispersed at high speed of 2500 rpm for 5-15 min.
  • the polyurethane adhesive tape may be stored at room temperature.
  • Priplast 3162 (abbreviated as “3162” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Croda Chemical (Shanghai) Co., Ltd. (located in Shanghai, China), having a molecular weight of 1000.
  • Priplast 3172 (abbreviated as “3172” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Croda Chemical (Shanghai) Co., Ltd. (located in Shanghai, China), having a molecular weight of 3000.
  • Priplast 3192 (abbreviated as “3192” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Croda Chemical (Shanghai) Co., Ltd. (located in Shanghai, China), having a molecular weight of 2000.
  • Priplast 3190 (abbreviated as “3190” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Croda Chemical (Shanghai) Co., Ltd. (located in Shanghai, China), having a molecular weight of 2000.
  • XCPA-110 (abbreviated as “110” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Xuchuan Chemical (Suzhou) Co., Ltd. (located in Suzhou, China), having a molecular weight of 1000.
  • XCPA-195 (abbreviated as “195” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Xuchuan Chemical (Suzhou) Co., Ltd. (located in Suzhou, China), having a molecular weight of 560.
  • XCP-1000N (abbreviated as “1000N” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Xuchuan Chemical (Suzhou) Co., Ltd. (located in Suzhou, China), having a molecular weight of 1000.
  • XCP-500N (abbreviated as “500N” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Xuchuan Chemical (Suzhou) Co., Ltd. (located in Suzhou, China), having a molecular weight of 500.
  • Pripol 2033 (abbreviated as “2033” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Croda Chemical (Shanghai) Co., Ltd. (located in Shanghai, China), having a molecular weight of 570.
  • Capa 3031 (abbreviated as “3031” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), aliphatic polycaprolactone triol, Perstorp UK Ltd. (located in Cheshire, UK), having a molecular weight of 300.
  • DesmodurN3800 (abbreviated as “N3800” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), Covestro (located in Shanghai, China).
  • DesmodurN3390 (abbreviated as “N3390” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 90 wt%), Covestro (located in Shanghai, China).
  • Desmodur Z4470 (abbreviated as “Z4470” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 70 wt%), Covestro (located in Shanghai, China).
  • PI film polyimide film
  • Ningbo Jinshan Electronic Materials Co., Ltd. located in Ningbo, China.
  • MEK methyl ethyl ketone
  • Sinopharm Shanghai Co., Ltd. located in Shanghai, China
  • analytical grade
  • MIBK methyl isobutyl ketone
  • Sinopharm Shanghai Co., Ltd. located in Shanghai, China
  • analytical grade
  • room-temperature adhesion test room-temperature 180° peeling force test
  • the surface of a substrate such as glass substrate, silicon wafer substrate, or stainless steel substrate
  • IP A isopropanol
  • the adhesive tape was laminated onto the surface of the substrate by rolling the adhesive tape back and forth once with an automatic roller (a roller press with an automatic roller, purchased from Chemlnstruments located in Fairfield, Ohio, USA) at a load of 4.5 pounds and speed of 12 in/min.
  • an automatic roller a roller press with an automatic roller, purchased from Chemlnstruments located in Fairfield, Ohio, USA
  • the adhesive tape test sample laminated onto the surface of the substrate was placed at room temperature (23°C) for 20 min, then Instron (180° peeling force tester, purchased from Instron located in Boston, USA) was used to test the room-temperature 180° peeling force of the adhesive tape test sample on the surface of the substrate at speed of 12 in/min, and the numerical value of the measured room-temperature 180° peeling force was recorded.
  • Instron 180° peeling force tester, purchased from Instron located in Boston, USA
  • the surface of a substrate (such as glass substrate, silicon wafer substrate, or stainless steel substrate) was cleaned by using isopropanol (IP A) and purging was performed by using compressed air to dry the surface of the substrate.
  • IP A isopropanol
  • the adhesive tape was laminated onto the surface of the substrate by rolling the adhesive tape back and forth once with an automatic roller (a roller press with an automatic roller, commercially available from Chemlnstruments located in Fairfield, Ohio, USA) at a load of 4.5 pounds and speed of 12 in/min.
  • the substrate with the laminated adhesive tape test sample was put into a muffle furnace (VULCAN 3-550 muffle furnace commercially available from Densply International located in York, Pennsylvania, USA), the temperature of the furnace was increased from room temperature to preset temperature (for example, 230°C, or 260°C) at speed of 35°C/min, and the preset temperature was kept for a period of time (for example, 10 min, 30 min, or lh).
  • the substrate with the laminated adhesive tape test sample was removed from the muffle furnace and cooled to room temperature, and whether blistering, bursting or falling -off appeared in the adhesive tape test sample was observed.
  • A weight of silica particles
  • A/B (weight of silica particles) / (weight of polydiol + weight of aliphatic polycaprolactone triol + weight of polydiisocyanate).
  • the weight of the polydiol, the weight of the aliphatic polycaprolactone triol and the weight of the polydiisocyanate may be respectively calculated according to the following formulas:
  • Weight of polydiol weight of polydiol solution c solid content of polydiol solution
  • Weight of aliphatic polycaprolactone triol weight of aliphatic polycaprolactone triol solution c solid content of aliphatic polycaprolactone triol solution
  • Weight of polydiisocyanate weight of polydiisocyanate solution c solid content of polydiisocyanate solution.
  • a PI fdm with thickness of 25 pm was cut into the size of A4 paper.
  • the second solution i.e., polyurethane adhesive solution
  • the PI film was put into an oven, heated from 120°C to 150°C, and kept at 150°C for 20 min for drying and curing, so as to obtain a polyurethane adhesive tape.
  • the polyurethane adhesive tape was subjected to room-temperature 180° peeling force test (surface of glass substrate) and high-temperature resistance test (surface of glass substrate, after 10 min at 260°C).
  • the test results were listed in Table 1-2.
  • Examples E2-E15 Polyurethane adhesive tapes in examples E2-E15 were prepared by adopting the same method as that in example El . The difference was that the components of the polyurethane adhesive composition used for preparing the polyurethane adhesive tapes and the content thereof were different, or the thickness of the polyurethane adhesive was different. The details were listed in Table 1-1 and Table 1-2. According to the test methods described herein, the polyurethane adhesive tapes in examples E1-E15 were subjected to room-temperature 180° peeling force test (surface of glass substrate) and high-temperature resistance test (surface of glass substrate, after 10 min at 260°C). The test results were listed in Table 1-2. Table 1-1
  • A/B (weight of silica particles) / (weight of polydiol + weight of aliphatic polycaprolactone triol + weight of polydiisocyanate).
  • the adhesive tapes prepared by using the polyurethane adhesive composition not only have good adhesion to the glass surface at room temperature, but also have good high-temperature resistance (after 10 min at 260°C, there is no blistering, bursting or falling off, and there is no adhesive residue on the surface of the glass substrate).
  • a PI film with thickness of 25 pm was cut into the size of A4 paper.
  • the second solution i.e., polyurethane adhesive solution
  • the PI film was put into an oven, heated from 120°C to 150°C for drying and curing, and kept at 150°C for 20 min, so as to obtain a polyurethane adhesive tape.
  • the polyurethane adhesive tape was subjected to room-temperature 180° peeling force test (surface of silicon wafer substrate) and high-temperature resistance test (surface of silicon wafer substrate). The test results were listed in Table 2-2.
  • Polyurethane adhesive tapes in examples E17-E23 and comparative example Cl were prepared by adopting the same method as that in example El 6. The difference was that the components of the polyurethane adhesive composition used for preparing the polyurethane adhesive tapes and the content thereof were different, or the thickness of the polyurethane adhesive was different. The details were listed in Table 2-1 and Table 2-2.
  • the polyurethane adhesive tapes were subjected to room-temperature 180° peeling force test (surface of silicon wafer substrate) and high-temperature resistance test (surface of silicon wafer substrate). The test results were listed in Table 2-2.
  • the adhesive tapes prepared by using the polyurethane adhesive composition not only have good adhesion to the surface of the silicon wafer substrate at room temperature, but also have good high-temperature resistance (after 60 min at 230°C, the adhesion to the surface of the silicon wafer substrate is still good, there is no blistering, bursting or falling off, and there is no adhesive residue on the surface of the silicon wafer substrate).
  • the polyurethane adhesive composition did not contain silica particles, so the polyurethane adhesive and adhesive tape prepared by using it failed to pass the high-temperature resistance test.
  • Example E24
  • a PI film with thickness of 25 pm was cut into the size of A4 paper.
  • the second solution i.e., polyurethane adhesive solution
  • the PI film was put into an oven, heated from 120°C to 150°C for drying and curing, and kept at 150°C for 20 min, so as to obtain a polyurethane adhesive tape.
  • the polyurethane adhesive tape was subjected to room-temperature 180° peeling force test (surface of stainless steel substrate) and high-temperature resistance test (surface of stainless steel substrate, after lh at 260°C).
  • the test results were listed in Table 3-2.
  • Polyurethane adhesive tapes in examples E25-E32 and comparative example C2 were prepared by adopting the same method as that in example E24. The difference was that the components of the polyurethane adhesive composition used for preparing the polyurethane adhesive tapes and the content thereof were different, or the thickness of the polyurethane adhesive was different. The details were listed in Table 3-1 and Table 3-2. According to the test methods described herein, the polyurethane adhesive tapes in examples E25-E32 and comparative example C2 were subjected to room -temperature 180° peeling force test (surface of stainless steel substrate) and high-temperature resistance test (surface of stainless steel substrate, after lh at 260°C). The test results were listed in Table 3-2.
  • A/B (weight of silica particles) / (weight of polydiol + weight of aliphatic polycaprolactone triol + weight of polydiisocyanate).
  • the adhesive tapes prepared by using the polyurethane adhesive composition provided by the present invention not only have good adhesion to the surface of the stainless steel substrate at room temperature, but also have good high-temperature resistance (after 60 min at 260°C, the adhesion to the surface of the stainless steel substrate is still good, there is no blistering, bursting or falling off, and there is no adhesive residue on the surface of the stainless steel substrate).
  • the polyurethane adhesive composition only contained polyester diol but did not contain aliphatic polycaprolactone triol, so the polyurethane adhesive and adhesive tape prepared by using it failed to pass the high-temperature resistance test.
  • the polyurethane adhesive prepared by using the polyurethane adhesive composition provided by the present invention at least has good low-temperature adhesion performance and good high-temperature resistance.
  • Solution 1 A polyurethane adhesive composition, including: a) apolydiol, at least including a polyester diol having a weight average molecular weight of 400-4000; b) an aliphatic polycaprolactone triol having a weight average molecular weight of 100-600; and c) a polydiisocyanate, at least including one of a hexamethylene diisocyanate trimer and an isophorone diisocyanate trimer.
  • Solution 2 The polyurethane adhesive composition according to solution 1, wherein the polyester diol at least includes one of an aromatic polyester diol and a fatty acid based polyester diol.
  • Solution 3 The polyurethane adhesive composition according to solution 1 or 2, wherein the polyester diol has a weight average molecular weight of 500-3000.
  • Solution 4 The polyurethane adhesive composition according to any one of the preceding solutions, wherein the aliphatic polycaprolactone triol has a weight average molecular weight of 200-400.
  • Solution 5 The polyurethane adhesive composition according to any one of the preceding solutions, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01-1:0.7.
  • Solution 6 The polyurethane adhesive composition according to any one of the preceding solutions, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.04-1:0.5.
  • Solution 7 The polyurethane adhesive composition according to any one of the preceding solutions, wherein the polydiol further includes a dimer diol.
  • Solution 8 The polyurethane adhesive composition according to solution 7, wherein the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1 : 1.
  • Solution 9 The polyurethane adhesive composition according to solution 7 or 8, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1 :0.04-l :0.3, and the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1:1.
  • Solution 10 The polyurethane adhesive composition according to any one of the preceding solutions, wherein the polyurethane adhesive composition further includes d) silica particles.
  • Solution 11 The polyurethane adhesive composition according to solution 10, wherein the average particle size of the silica particles is 5-15 pm.
  • Solution 12 The polyurethane adhesive composition according to solution 10 or 11, wherein the silica particles at least include one of polydimethylsiloxane surface -modified silica particles, wax surface -modified silica particles, and surface-unmodified silica particles.
  • Solution 13 The polyurethane adhesive composition according to solution 10, 11 or 12, wherein the ratio of the weight of the silica particles to the total weight of the polydiol, aliphatic polycaprolactone triol, and polydiisocyanate is 1.0: 100-5.1: 100.
  • Solution 14 A polyurethane adhesive, including a cured product of the polyurethane adhesive composition according to any one of solutions 1-13.
  • Solution 15 A polyurethane adhesive tape, including a substrate and the polyurethane adhesive according to solution 14 disposed on the substrate.
  • Solution 16 The polyurethane adhesive tape according to solution 15, wherein the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, release paper, or a release film.
  • Solution 17 A method for preparing a polyurethane adhesive tape, including the following steps: disposing the polyurethane adhesive composition according to any one of solutions 1-13 on a substrate; and curing the polyurethane adhesive composition.

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Abstract

The present invention relates to a polyurethane adhesive composition, including: a) a polydiol, at least including a polyester diol having a weight average molecular weight of 400-4000; b) an aliphatic polycaprolactone triol having a weight average molecular weight of 100-600; and c) a polydiisocyanate, at least including one of a hexamethylene diisocyanate trimer and an isophorone diisocyanate trimer. A polyurethane adhesive prepared from the polyurethane adhesive composition provided by the present invention and a polyurethane adhesive tape including the polyurethane adhesive at least have good room-temperature adhesion performance and good high-temperature resistance.

Description

A POLYURETHANE ADHESIVE COMPOSITION, A POLYURETHANE ADHESIVE, A POLYURETHANE ADHESIVE TAPE, AND THE METHOD FOR PREPARING THE POLYURETHANE ADHESIVE TAPE
Technical Field
The present invention relates to the field of adhesives, in particular to a polyurethane adhesive composition, a polyurethane adhesive, an adhesive tape including the polyurethane adhesive, and a method for preparing the adhesive tape. Background
With the emergence and rapid development of electric vehicles, sensors, VR/AR (Virtual Reality/ Augmented Reality), Internet of Things, block chains, 5G technologies and the like, the chip market is growing rapidly. In the chip manufacturing process, it is often necessary to use a protective film to protect a chip. For example, in the chip thinning process, a protective film is needed to protect a chi. For another example, in some chip processes involving high temperature (such as tin ball and copper column deposition processes), a protective film is also needed to protect a chip from 200°C or higher temperature (even more than 260°C) for several minutes to dozens of minutes. Therefore, it is necessary to provide a protective film with good adhesion performance at room temperature and high-temperature resistance to meet this demand.
In addition, the deposition of high-performance coatings can be used to improve the optical properties of glass screens in the display manufacturing process. In order to keep the coatings smooth on an atomic scale, it is necessary to prepare the coatings through a vapor deposition process. Generally, in the vapor deposition process (generally, they must be deposited at 200°C or more than 200°C), a protective film is needed to protect regions on a glass screen where coatings are not needed to be coated. In addition, in the vapor deposition process, this protective film must have good adhesion performance with a substrate, so as to avoid blistering, warping and falling off. In addition, after the vapor deposition process, the protective film must be easily removed without leaving residual adhesives on the substrate. Therefore, it is necessary to provide a protective film with good adhesion performance at room temperature and high-temperature resistance to meet this demand.
Summary
One purpose of the present invention is to provide a polyurethane adhesive composition and a polyurethane adhesive based on the composition. The polyurethane adhesive at least has good room-temperature adhesion performance and high-temperature resistance, so it can be used to solve some problems in the process of manufacturing chips or display glass screens.
Another purpose of the present invention is to provide a polyurethane adhesive tape.
Another purpose of the present invention is to provide a method for preparing a polyurethane adhesive tape.
For these purposes, in one aspect, the present invention provides a polyurethane adhesive composition, including: a) a polydiol, at least including a polyester diol having a weight average molecular weight of 400-4000; b) an aliphatic polycaprolactone triol having a weight average molecular weight of 100-600; and c) a polydiisocyanate, at least including one of a hexamethylene diisocyanate trimer and an isophorone diisocyanate trimer.
According to some technical solutions of the present invention, the polyester diol at least includes one of an aromatic polyester diol and a fatty acid based polyester diol.
According to some technical solutions of the present invention, the polyester diol has a weight average molecular weight of 500-3000.
According to some technical solutions of the present invention, the aliphatic polycaprolactone triol has a weight average molecular weight of 200-400.
According to some technical solutions of the present invention, the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01-1:0.7, preferably 1:0.04-1:0.5, particularly preferably 1:0.06-1:0.3. According to some technical solutions of the present invention, the polydiol further includes a dimer diol.
According to some technical solutions of the present invention, the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1 : 1.
According to some technical solutions of the present invention, the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1 :0.04-l :0.3, and the weight ratio of the polyester diol to the dimer diol is 1:0.1-1: 1; preferably, the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.06-1:0.3, and the weight ratio of the polyester diol to the dimer diol is 1:0.1-1: 1.
According to some technical solutions of the present invention, the polyurethane adhesive composition further includes d) silica particles.
According to some technical solutions of the present invention, the average particle size (D50) of the silica particles is 5-15 pm, preferably 6-10 pm.
According to some technical solutions of the present invention, the silica particles at least include one of polydimethylsiloxane (PDMS) surface-modified silica particles, wax surface -modified silica particles, and surface-unmodified silica particles.
According to some technical solutions of the present invention, the ratio of the weight of the silica particles to the total weight of the polydiol, aliphatic polycaprolactone triol and polydiisocyanate is 1.0: 100-5.1: 100.
In another aspect, the present invention provides a polyurethane adhesive, including a cured product of the polyurethane adhesive composition provided by the present invention.
According to another aspect, the present invention provides an adhesive tape, including a substrate and the polyurethane adhesive provided by the present invention disposed on the substrate. According to some technical solutions of the present invention, the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, release paper, or a release film.
In another aspect, the present invention provides a method for preparing a polyurethane adhesive tape, including the following steps: disposing the polyurethane adhesive composition provided by the present invention on a substrate; and curing the polyurethane adhesive composition.
Hereinafter, the present invention will be described in more detail in combination with the detailed description of the present invention.
Detailed Description
Hereinafter, in order to describe the present invention more clearly, several technical solutions of the present invention and several technical solutions for comparison are described. However, this section only exemplifies some specific embodiments claimed, in which the technical features recited in one or more technical solutions can be combined with any one or more technical solutions, and these technical solutions obtained by combination also fall within the protection scope of the present invention as long as they do not depart from the spirit of the present invention.
“Good room-temperature adhesion performance” used herein refers to that a polyurethane adhesive or polyurethane adhesive tape can be adhered to a surface of a substrate (including but not limited to a glass substrate, a stainless steel substrate, or a silicon wafer substrate) at room temperature (23°C), and has good room-temperature 180° peeling force on the substrate.
“Good high-temperature resistance” used herein refers to that after a high-temperature process, a polyurethane adhesive or a polyurethane adhesive tape can still be adhered to the substrate without blistering and falling off, and can be completely removed from the surface of the protected substrate without leaving residual adhesives. “Average particle size” used herein refers to the particle size of particles whose cumulative frequency (G or R) of particle size distribution is equal to 50%, also called as median diameter, also known as D50.
Polyurethane adhesive composition
A polyurethane adhesive composition provided by the present invention includes: a) a polydiol, at least including a polyester diol having a weight average molecular weight of 400-4000; b) an aliphatic polycaprolactone triol having a weight average molecular weight of 100-600; and c) a polydiisocyanate, at least including one of a hexamethylene diisocyanate trimer and an isophorone diisocyanate trimer.
In the present invention, the polyester diol refers to a polyester polyol with a hydroxyl functionality of 2 obtained through condensation reaction of a dicarboxylic acid, a diol, and the like. The polyester diol has a molecular weight of 400-4000, preferably 500-3000. The polyester diol can adjust the polarity and cohesive strength of the polyurethane adhesive, so as to adjust the room-temperature adhesion performance and high-temperature resistance of the polyurethane adhesive.
According to one embodiment of the present invention, the polyester diol may be a fatty acid based polyester diol. The fatty acid based polyester diol may be Priplast 3162, Priplast 3172, Priplast 3192, or Priplast 3190 purchased from Croda Chemical (Shanghai) Co., Ltd. located in Shanghai, China.
According to one embodiment of the present invention, the polyester diol may also be an aromatic polyester diol. The aromatic polyester diol maybe X CPA-110 orXCPA-195 purchased from of Xuchuan Chemical (Suzhou) Co., Ltd. located in Suzhou, China.
According to one embodiment of the present invention, the polydiol may further include a dimer diol. The dimer diol may be prepared through hydrogenation reduction of dimer acid. The dimer acid may be a complex mixture consisting of Cl 8 unsaturated fatty acid dimers with different structures and higher oligomers. The dimer diol can adjust the polarity and cohesive strength of the polyurethane adhesive, so as to adjust the room-temperature adhesion performance and high-temperature resistance of the polyurethane adhesive.
According to one embodiment of the present invention, the dimer diol may be Pripol 2033 or Pripol 2030 purchased from Croda Chemical (Shanghai) Co., Ltd. located in Shanghai, China.
According to one embodiment of the present invention, the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1 : 1. When the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1 : 1, the polyurethane adhesive can have good high-temperature resistance.
In the present invention, the aliphatic polycaprolactone triol refers to a polyester polyol with a hydroxyl functionality of 3 formed through ring -opening polymerization of caprolactone, and the aliphatic polycaprolactone triol has a weight average molecular weight of 100-600, preferably 200-400. The aliphatic polycaprolactone triol can increase the cross-linking degree of the polyurethane adhesive, thereby improving the high-temperature resistance of the polyurethane adhesive.
According to one embodiment of the present invention, the aliphatic polycaprolactone triol may be Capa 3050 or Capa 3031 purchased from Perstorp UK Ltd. located in Cheshire, UK.
According to one embodiment of the present invention, the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01-1:0.7, preferably 1:0.04-1:0.5. When the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01-1:0.7, the polyurethane adhesive can have good high-temperature resistance.
According to one embodiment of the present invention, the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1 :0.01-1 :0.7, preferably 1 :0.04-l :0.5, and the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1 : 1. At this time, the polyurethane adhesive can have good high-temperature resistance. In the present invention, the polydiisocyanate at least includes one of a hexamethylene diisocyanate trimer and an isophorone diisocyanate trimer. The hexamethylene diisocyanate trimer and isophorone diisocyanate trimer can provide good room-temperature adhesion performance and high-temperature resistance for the polyurethane adhesive.
According to one embodiment of the present invention, the hexamethylene diisocyanate trimer may be N3800, N3390 or N3300 purchased from Covestro located in Shanghai, China.
According to one embodiment of the present invention, the isophorone diisocyanate trimer may be Z4470 purchased from Covestro located in Shanghai, China.
According to some technical solutions of the present invention, the polyurethane adhesive composition provided by the present invention may further include silica particles. In the present invention, the average particle size D50 of the silica particles is 5-15 pm, preferably 6-10 pm. The silica particles can adjust the room-temperature adhesion performance of the polyurethane adhesive and improve the high-temperature resistance of the polyurethane adhesive.
According to one embodiment of the present invention, the silica particles may be one or more selected from the group consisting of polydimethylsiloxane (PDMS) surface -modified silica particles, wax surface-modified silica particles, and surface-unmodified silica particles.
According to one embodiment of the present invention, the polydimethylsiloxane (PDMS) surface-modified silica particles may be Acematt 3300 purchased from Evonik located in Shanghai, China. According to one embodiment of the present invention, the wax surface -modified silica particles may be OK520 purchased from Evonik located in Shanghai, China. According to one embodiment of the present invention, the surface-unmodified silica particles may be TS-100 purchased from Evonik located in Shanghai, China. According to one embodiment of the present invention, in the polyurethane adhesive composition provided by the present invention, the ratio of the weight of the silica particles to the total weight of the polydiol, aliphatic polycaprolactone triol and polydiisocyanate is 1.0:100-5.1:100. The ratio (A/B) may be calculated according to the following formula:
A = weight of silica particles,
B = weight of polydiol + weight of aliphatic polycaprolactone triol + weight of polydiisocyanate,
A/B = (weight of silica particles) / (weight of polydiol + weight of aliphatic polycaprolactone triol + weight of polydiisocyanate).
The weight of the polydiol, the weight of the aliphatic polycaprolactone triol and the weight of the polydiisocyanate may be respectively calculated according to the following formulas:
Weight of polydiol = weight of polydiol solution c solid content of polydiol solution,
Weight of aliphatic polycaprolactone triol = weight of aliphatic polycaprolactone triol solution c solid content of aliphatic polycaprolactone triol solution,
Weight of polydiisocyanate = weight of polydiisocyanate solution c solid content of polydiisocyanate solution.
Polyurethane adhesive
A polyurethane adhesive provided by the present invention includes a cured product of the polyurethane adhesive composition provided by the present invention.
Components of the polyurethane adhesive composition are detailed in the “Polyurethane adhesive composition” in this description, and thus will not be repetitively described here.
According to one embodiment of the present invention, the polyurethane adhesive may be prepared according to the following steps: step 1 : adding all component of the polyurethane adhesive composition into a suitable container for mixing at room temperature; step 2: putting the all mixed components of the polyurethane adhesive composition into an oven for reaction and curing to obtain a polyurethane adhesive.
According to one embodiment of the present invention, in step 2, after the mixed components of the polyurethane adhesive composition are put into the oven, the temperature is increased from 120°C to 150°C and kept for 20 min to enable the polyurethane adhesive composition to react and be cured to obtain the polyurethane adhesive.
According to one embodiment of the present invention, in step 2, after the mixed components of the polyurethane adhesive composition are put into the oven, the temperature may be increased from 120°C to 150°C and kept for 20 min, and then the temperature may be decreased to 80°C and kept for 24h to complete the curing reaction.
According to one embodiment of the present invention, in step 1, all components of the polyurethane adhesive composition except silica particles may be first added into a suitable container, and then the silica particles may be added into the container and dispersed at high speed of 2500 rpm for 5-15 min.
According to one embodiment of the present invention, the polyurethane adhesive may be stored at room temperature.
According to one embodiment of the present invention, the polyurethane adhesive provided by the present invention at least has good room-temperature adhesion performance and good high-temperature resistance.
According to one embodiment of the present invention, when the polyurethane adhesive composition provided by the present invention includes an appropriate amount of polydiol, aliphatic polycaprolactone triol and polydiisocyanate, the polyurethane adhesive prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a glass substrate.
According to one embodiment of the present invention, when the polyurethane adhesive provided by the present invention includes an appropriate amount of polydiol, aliphatic polycaprolactone triol, polydiisocyanate and silica particles, the polyurethane adhesive prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a silicon wafer substrate.
According to one embodiment of the present invention, when the polyurethane adhesive provided by the present invention includes an appropriate amount of polydiol, aliphatic polycaprolactone triol, polydiisocyanate and silica particles, the polyurethane adhesive prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a stainless steel substrate.
Polyurethane adhesive tape
An adhesive tape (also called “protective film”) provided by the present invention includes a substrate and a polyurethane adhesive provided by the present invention disposed on the substrate. The polyurethane adhesive is detailed in the “Polyurethane adhesive” in this description, and thus will not be repetitively described here.
According to one embodiment of the present invention, the polyurethane adhesive may be provided on at least one side of the substrate.
According to one embodiment of the present invention, the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, release paper, or a release fdm. According to one embodiment of the present invention, the polyurethane adhesive provided by the present invention at least has good room-temperature adhesion performance and good high-temperature resistance.
According to one embodiment of the present invention, when the polyurethane adhesive composition provided by the present invention includes an appropriate amount of polydiol, aliphatic polycaprolactone triol and polydiisocyanate, the polyurethane adhesive tape prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a glass substrate.
According to one embodiment of the present invention, when the polyurethane adhesive provided by the present invention includes an appropriate amount of polydiol, aliphatic polycaprolactone triol, polydiisocyanate and silica particles, the polyurethane adhesive tape prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a silicon wafer substrate.
According to one embodiment of the present invention, when the polyurethane adhesive provided by the present invention includes an appropriate amount of polydiol, aliphatic polycaprolactone triol, polydiisocyanate and silica particles, the polyurethane adhesive tape prepared by using the polyurethane adhesive composition has good room-temperature adhesion performance and good high-temperature resistance on the surface of a stainless steel substrate.
Method for preparing polyurethane adhesive tape
A method for preparing a polyurethane adhesive tape provided by the present invention includes the following steps: disposing the polyurethane adhesive composition provided by the present invention on a substrate; and curing the polyurethane adhesive composition. Components of the polyurethane adhesive composition are detailed in the “Polyurethane adhesive composition” in this description, and thus will not be repetitively described here.
According to one embodiment of the present invention, in particular, the preparation method may comprise the following steps: step 1 : adding all component of the polyurethane adhesive composition into a suitable container for mixing at room temperature; step 2: coating the mixed polyurethane adhesive composition on a surface of a substrate; and step 3 : putting the substrate coated with the polyurethane adhesive composition into an oven for reaction and curing to obtain a polyurethane adhesive.
According to one embodiment of the present invention, in step 3, after the substrate coated with the polyurethane adhesive composition is put into the oven, the temperature is increased from 120°C to 150°C and kept for 20 min to enable the polyurethane adhesive composition to react and be cured to obtain the polyurethane adhesive.
According to one embodiment of the present invention, in step 3, after the substrate coated with the polyurethane adhesive composition is put into the oven, the temperature may be increased from 120°C to 150°C and kept for 20 min, and then the temperature may be decreased to 80°C and kept for 24h to complete the curing reaction.
According to one embodiment of the present invention, in step 1, all components of the polyurethane adhesive composition except silica particles may be first added into a suitable container, and then the silica particles may be added into the container and dispersed at high speed of 2500 rpm for 5-15 min.
According to one embodiment of the present invention, the polyurethane adhesive tape may be stored at room temperature. Examples
Hereinafter, preferred examples will be provided to better understand the present invention. However, the following examples are used for exemplary description purpose only and for those skilled in the art to better understand the present invention. The present invention should not be limited by these examples.
1. Raw materials (1) Polyester diol
Priplast 3162 (abbreviated as “3162” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Croda Chemical (Shanghai) Co., Ltd. (located in Shanghai, China), having a molecular weight of 1000.
Priplast 3172 (abbreviated as “3172” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Croda Chemical (Shanghai) Co., Ltd. (located in Shanghai, China), having a molecular weight of 3000.
Priplast 3192 (abbreviated as “3192” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Croda Chemical (Shanghai) Co., Ltd. (located in Shanghai, China), having a molecular weight of 2000.
Priplast 3190 (abbreviated as “3190” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Croda Chemical (Shanghai) Co., Ltd. (located in Shanghai, China), having a molecular weight of 2000.
XCPA-110 (abbreviated as “110” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Xuchuan Chemical (Suzhou) Co., Ltd. (located in Suzhou, China), having a molecular weight of 1000.
XCPA-195 (abbreviated as “195” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Xuchuan Chemical (Suzhou) Co., Ltd. (located in Suzhou, China), having a molecular weight of 560. XCP-1000N (abbreviated as “1000N” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Xuchuan Chemical (Suzhou) Co., Ltd. (located in Suzhou, China), having a molecular weight of 1000.
XCP-500N (abbreviated as “500N” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Xuchuan Chemical (Suzhou) Co., Ltd. (located in Suzhou, China), having a molecular weight of 500.
(2) Dimer diol
Pripol 2033 (abbreviated as “2033” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), polyester diol, Croda Chemical (Shanghai) Co., Ltd. (located in Shanghai, China), having a molecular weight of 570.
(3) Aliphatic polycaprolactone triol
Capa 3031 (abbreviated as “3031” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), aliphatic polycaprolactone triol, Perstorp UK Ltd. (located in Cheshire, UK), having a molecular weight of 300.
(4) Hexamethylene diisocyanate trimer
DesmodurN3800 (abbreviated as “N3800” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 100 wt%), Covestro (located in Shanghai, China).
DesmodurN3390 (abbreviated as “N3390” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 90 wt%), Covestro (located in Shanghai, China).
(5) Isophorone diisocyanate trimer
Desmodur Z4470 (abbreviated as “Z4470” in Table 1-1, Table 2-1, and Table 3-1, with solid content of 70 wt%), Covestro (located in Shanghai, China).
(6) Silica particles
TS-100, silica particles, Evonik (located in Shanghai, China), average diameter D50 = 6.5 pm.
Acematt 3300, polydimethylsiloxane (PDMS) surface -modified silica particles, Evonik (located in Shanghai, China), average diameter D50 = 10 pm. EXP 3400, polydimethylsiloxane (PDMS) surface-modified silica particles, Evonik (located in Shanghai, China), average diameter D50 = 6.5 pm.
OK-520, wax surface -modified silica particles, Evonik (located in Shanghai, China), average diameter D50 = 6.5 pm.
(7) Substrate
PI film (polyimide film), Ningbo Jinshan Electronic Materials Co., Ltd. (located in Ningbo, China).
(8) Others
MEK (methyl ethyl ketone), Sinopharm Shanghai Co., Ltd. (located in Shanghai, China), analytical grade.
Dibutyltin dilaurate (DBTDL), Sinopharm Shanghai Co., Ltd. (located in Shanghai,
China).
Propylene glycol 1-monomethyl ether 2-acetate, Dow Chemical Co., Ltd. (located in Shanghai, China).
MIBK (methyl isobutyl ketone), Sinopharm Shanghai Co., Ltd. (located in Shanghai, China), analytical grade.
BA (butyl acetate), Sinopharm Shanghai Co., Ltd. (located in Shanghai, China), analytical grade.
Xylene, Sinopharm Shanghai Co., Ltd. (located in Shanghai, China), analytical grade.
Acetyl acetone, Sinopharm Shanghai Co., Ltd. (located in Shanghai, China), analytical grade.
2. Test methods
(1) Room-temperature adhesion test (room-temperature 180° peeling force test) The surface of a substrate (such as glass substrate, silicon wafer substrate, or stainless steel substrate) was cleaned by using isopropanol (IP A) and purging was performed by using compressed air to dry the surface of the substrate.
Cutting was performed to obtain a rectangular adhesive tape test sample with width of 1 inch.
The adhesive tape was laminated onto the surface of the substrate by rolling the adhesive tape back and forth once with an automatic roller (a roller press with an automatic roller, purchased from Chemlnstruments located in Fairfield, Ohio, USA) at a load of 4.5 pounds and speed of 12 in/min.
The adhesive tape test sample laminated onto the surface of the substrate was placed at room temperature (23°C) for 20 min, then Instron (180° peeling force tester, purchased from Instron located in Boston, USA) was used to test the room-temperature 180° peeling force of the adhesive tape test sample on the surface of the substrate at speed of 12 in/min, and the numerical value of the measured room-temperature 180° peeling force was recorded.
(2) High-temperature resistance test
The surface of a substrate (such as glass substrate, silicon wafer substrate, or stainless steel substrate) was cleaned by using isopropanol (IP A) and purging was performed by using compressed air to dry the surface of the substrate.
Cutting was performed to obtain a rectangular adhesive tape test sample with width of 1 inch.
The adhesive tape was laminated onto the surface of the substrate by rolling the adhesive tape back and forth once with an automatic roller (a roller press with an automatic roller, commercially available from Chemlnstruments located in Fairfield, Ohio, USA) at a load of 4.5 pounds and speed of 12 in/min. The substrate with the laminated adhesive tape test sample was put into a muffle furnace (VULCAN 3-550 muffle furnace commercially available from Densply International located in York, Pennsylvania, USA), the temperature of the furnace was increased from room temperature to preset temperature (for example, 230°C, or 260°C) at speed of 35°C/min, and the preset temperature was kept for a period of time (for example, 10 min, 30 min, or lh).
The substrate with the laminated adhesive tape test sample was removed from the muffle furnace and cooled to room temperature, and whether blistering, bursting or falling -off appeared in the adhesive tape test sample was observed.
Then the adhesive tape test sample was manually pulled up from the laminated substrate to observe whether there was adhesive residue on the surface of the substrate.
If no blistering, bursting or falling off appeared on the adhesive tape test sample and no adhesive residue was left on the surface of the substrate, it was marked as “good”. Otherwise, it was marked as “unacceptable”.
Example El
1.00 g of propylene glycol 1-monomethyl ether 2-acetate, 1.58 g of butyl acetate (BA), 0.54 g ofmethyl isobutyl ketone (MIBK), 0.98 g ofxylene, 1.77 g of XCPA-110, 1.61 g of XCPA-195, 0.40 g of CAPA-3031, 0.15 g of 1 wt% DBTDL MEK solution, and 0.30 g of acetylacetone were added into a 30 ml plastic bottle. Then, a plastic bottle cap was tightly closed and put into a high-speed mixer ARE-310 (commercially available from Thinky located in Tokyo, Japan). First, mixing was performed for 2 min at speed of 2000 rpm. Then, defoaming was performed for 2 min at speed of 2200 rpm, so as to obtain uniform first solution.
Then, 5.22 g ofN3800 and 0.24 g of TS-100 were added to the first solution. Stirring was performed for 5 min on a high-speed disperser SFJ-400 (commercially available from Shanghai Modem Environmental Engineering Technology Co., Ltd. located in Shanghai, China) at speed of 2500 rpm to obtain uniform second solution (i.e., polyurethane adhesive solution). The components of the second solution and the content thereof were as shown in Table 1-1. For example, in this example, the molar ratio ofNCO:OH was 1.034: 1. Moreover, the ratio of the weight of silica particles to the total weight of polydiol, aliphatic polycaprolactone triol and polydiisocyanate was 2.67: 100. The specific calculation formula of the ratio (A/B) was as follows:
A = weight of silica particles,
A/B = (weight of silica particles) / (weight of polydiol + weight of aliphatic polycaprolactone triol + weight of polydiisocyanate).
The weight of the polydiol, the weight of the aliphatic polycaprolactone triol and the weight of the polydiisocyanate may be respectively calculated according to the following formulas:
Weight of polydiol = weight of polydiol solution c solid content of polydiol solution,
Weight of aliphatic polycaprolactone triol = weight of aliphatic polycaprolactone triol solution c solid content of aliphatic polycaprolactone triol solution,
Weight of polydiisocyanate = weight of polydiisocyanate solution c solid content of polydiisocyanate solution.
In example 1, A/B = 0.24/(1.77c 100%+1.61c 100%+0.40c 100%+5.22c 100%)= 2.67/100.
A PI fdm with thickness of 25 pm was cut into the size of A4 paper.
The second solution (i.e., polyurethane adhesive solution) was coated on the PI film with a comma roller. The PI film was put into an oven, heated from 120°C to 150°C, and kept at 150°C for 20 min for drying and curing, so as to obtain a polyurethane adhesive tape.
According to the test methods described herein, the polyurethane adhesive tape was subjected to room-temperature 180° peeling force test (surface of glass substrate) and high-temperature resistance test (surface of glass substrate, after 10 min at 260°C). The test results were listed in Table 1-2.
Examples E2-E15 Polyurethane adhesive tapes in examples E2-E15 were prepared by adopting the same method as that in example El . The difference was that the components of the polyurethane adhesive composition used for preparing the polyurethane adhesive tapes and the content thereof were different, or the thickness of the polyurethane adhesive was different. The details were listed in Table 1-1 and Table 1-2. According to the test methods described herein, the polyurethane adhesive tapes in examples E1-E15 were subjected to room-temperature 180° peeling force test (surface of glass substrate) and high-temperature resistance test (surface of glass substrate, after 10 min at 260°C). The test results were listed in Table 1-2. Table 1-1
Figure imgf000020_0001
Figure imgf000021_0001
• Note 1 : A/B = (weight of silica particles) / (weight of polydiol + weight of aliphatic polycaprolactone triol + weight of polydiisocyanate).
Table 1-2
Figure imgf000021_0002
According to examples El -El 5, when the polyurethane adhesive composition provided by the present invention includes an appropriate amount of polydiol, aliphatic polycaprolactone triol and polydiisocyanate, the adhesive tapes prepared by using the polyurethane adhesive composition not only have good adhesion to the glass surface at room temperature, but also have good high-temperature resistance (after 10 min at 260°C, there is no blistering, bursting or falling off, and there is no adhesive residue on the surface of the glass substrate).
Example El 6
61.63 g of MEK (methyl ethyl ketone), 24.17 g of XCPA-110, 24.17 g ofXCPA-195, 6.36 g of CAPA-3031, and 2.27 g of 1 wt% DBTDL MEK solution were added into a 500 ml plastic container and uniformly mixed to obtain uniform first solution.
Then, 78.30 g of N3800 and 2.78 g of Acematt 3300 were added to the first solution. Stirring was performed for 5 min on a high-speed disperser SFJ-400 (commercially available from Shanghai Modem Environmental Engineering Technology Co., Ltd. located in Shanghai, China) at speed of 2500 rpm to obtain uniform second solution (i.e., polyurethane adhesive solution). The components of the second solution and the content thereof were as shown in Table 2-1. For example, in this example, the molar ratio of NCO:OH was 1.034: 1; and A/B = 2.09/100.
A PI film with thickness of 25 pm was cut into the size of A4 paper.
The second solution (i.e., polyurethane adhesive solution) was coated on the PI film with a comma roller. The PI film was put into an oven, heated from 120°C to 150°C for drying and curing, and kept at 150°C for 20 min, so as to obtain a polyurethane adhesive tape.
According to the test methods described herein, the polyurethane adhesive tape was subjected to room-temperature 180° peeling force test (surface of silicon wafer substrate) and high-temperature resistance test (surface of silicon wafer substrate). The test results were listed in Table 2-2.
Examples E17-E23 and comparative example Cl
Polyurethane adhesive tapes in examples E17-E23 and comparative example Cl were prepared by adopting the same method as that in example El 6. The difference was that the components of the polyurethane adhesive composition used for preparing the polyurethane adhesive tapes and the content thereof were different, or the thickness of the polyurethane adhesive was different. The details were listed in Table 2-1 and Table 2-2.
According to the test methods described herein, the polyurethane adhesive tapes were subjected to room-temperature 180° peeling force test (surface of silicon wafer substrate) and high-temperature resistance test (surface of silicon wafer substrate). The test results were listed in Table 2-2.
Table 2-1
Figure imgf000023_0001
· Note 2: A/B = (weight of silica particles) / (weight of polydiol + weight of aliphatic polycaprolactone triol + weight of polydiisocyanate).
Table 2-2
Figure imgf000024_0001
According to examples E16-E23, when the polyurethane adhesive composition provided by the present invention includes an appropriate amount of polydiol, aliphatic polycaprolactone triol, polydiisocyanate and silica particles, the adhesive tapes prepared by using the polyurethane adhesive composition not only have good adhesion to the surface of the silicon wafer substrate at room temperature, but also have good high-temperature resistance (after 60 min at 230°C, the adhesion to the surface of the silicon wafer substrate is still good, there is no blistering, bursting or falling off, and there is no adhesive residue on the surface of the silicon wafer substrate).
In comparative example Cl, the polyurethane adhesive composition did not contain silica particles, so the polyurethane adhesive and adhesive tape prepared by using it failed to pass the high-temperature resistance test. Example E24
46.18 g of MEK (methyl ethyl ketone), 18.09 g of Priplast 3162, 18.09 g of Pripol 2033, 4.76 g of CAPA-3031, and 1.70 g of 1 wt% DBTDL MEK solution were added into a 500 ml plastic container and uniformly mixed to obtain uniform first solution.
Then, 58.16 g of N3800 and 2.02 g of Acematt 3300 were added to the first solution. Stirring was performed for 5 min on a high-speed disperser SFJ-400 (commercially available from Shanghai Modem Environmental Engineering Technology Co., Ltd. located in Shanghai, China) at speed of 2500 rpm to obtain uniform second solution (i.e., polyurethane adhesive solution). The components of the second solution and the content thereof were as shown in Table 3-1. For example, in this example, the molar ratio of NCO:OH was 1.034: 1, and A/B = 2.04/100.
A PI film with thickness of 25 pm was cut into the size of A4 paper.
The second solution (i.e., polyurethane adhesive solution) was coated on the PI film with a comma roller. The PI film was put into an oven, heated from 120°C to 150°C for drying and curing, and kept at 150°C for 20 min, so as to obtain a polyurethane adhesive tape.
According to the test methods described herein, the polyurethane adhesive tape was subjected to room-temperature 180° peeling force test (surface of stainless steel substrate) and high-temperature resistance test (surface of stainless steel substrate, after lh at 260°C). The test results were listed in Table 3-2.
Examples E25-E32 and comparative example C2
Polyurethane adhesive tapes in examples E25-E32 and comparative example C2 were prepared by adopting the same method as that in example E24. The difference was that the components of the polyurethane adhesive composition used for preparing the polyurethane adhesive tapes and the content thereof were different, or the thickness of the polyurethane adhesive was different. The details were listed in Table 3-1 and Table 3-2. According to the test methods described herein, the polyurethane adhesive tapes in examples E25-E32 and comparative example C2 were subjected to room -temperature 180° peeling force test (surface of stainless steel substrate) and high-temperature resistance test (surface of stainless steel substrate, after lh at 260°C). The test results were listed in Table 3-2.
Table 3-1
Figure imgf000026_0001
Note 3 : A/B = (weight of silica particles) / (weight of polydiol + weight of aliphatic polycaprolactone triol + weight of polydiisocyanate).
Table 3-2
Figure imgf000027_0001
According to examples E24-E32, when the polyurethane adhesive composition provided by the present invention includes an appropriate amount of polydiol, aliphatic polycaprolactone triol, polydiisocyanate and silica particles, the adhesive tapes prepared by using the polyurethane adhesive composition provided by the present invention not only have good adhesion to the surface of the stainless steel substrate at room temperature, but also have good high-temperature resistance (after 60 min at 260°C, the adhesion to the surface of the stainless steel substrate is still good, there is no blistering, bursting or falling off, and there is no adhesive residue on the surface of the stainless steel substrate).
In comparative example Cl, the polyurethane adhesive composition only contained polyester diol but did not contain aliphatic polycaprolactone triol, so the polyurethane adhesive and adhesive tape prepared by using it failed to pass the high-temperature resistance test. To sum up, the polyurethane adhesive prepared by using the polyurethane adhesive composition provided by the present invention at least has good low-temperature adhesion performance and good high-temperature resistance.
According to the concept of the present invention, the inventor proposes at least the following technical solutions:
Solution 1: A polyurethane adhesive composition, including: a) apolydiol, at least including a polyester diol having a weight average molecular weight of 400-4000; b) an aliphatic polycaprolactone triol having a weight average molecular weight of 100-600; and c) a polydiisocyanate, at least including one of a hexamethylene diisocyanate trimer and an isophorone diisocyanate trimer.
Solution 2: The polyurethane adhesive composition according to solution 1, wherein the polyester diol at least includes one of an aromatic polyester diol and a fatty acid based polyester diol.
Solution 3 : The polyurethane adhesive composition according to solution 1 or 2, wherein the polyester diol has a weight average molecular weight of 500-3000.
Solution 4: The polyurethane adhesive composition according to any one of the preceding solutions, wherein the aliphatic polycaprolactone triol has a weight average molecular weight of 200-400.
Solution 5 : The polyurethane adhesive composition according to any one of the preceding solutions, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01-1:0.7.
Solution 6: The polyurethane adhesive composition according to any one of the preceding solutions, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.04-1:0.5. Solution 7 : The polyurethane adhesive composition according to any one of the preceding solutions, wherein the polydiol further includes a dimer diol. Solution 8: The polyurethane adhesive composition according to solution 7, wherein the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1 : 1.
Solution 9: The polyurethane adhesive composition according to solution 7 or 8, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1 :0.04-l :0.3, and the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1:1.
Solution 10: The polyurethane adhesive composition according to any one of the preceding solutions, wherein the polyurethane adhesive composition further includes d) silica particles.
Solution 11: The polyurethane adhesive composition according to solution 10, wherein the average particle size of the silica particles is 5-15 pm.
Solution 12: The polyurethane adhesive composition according to solution 10 or 11, wherein the silica particles at least include one of polydimethylsiloxane surface -modified silica particles, wax surface -modified silica particles, and surface-unmodified silica particles.
Solution 13: The polyurethane adhesive composition according to solution 10, 11 or 12, wherein the ratio of the weight of the silica particles to the total weight of the polydiol, aliphatic polycaprolactone triol, and polydiisocyanate is 1.0: 100-5.1: 100.
Solution 14: A polyurethane adhesive, including a cured product of the polyurethane adhesive composition according to any one of solutions 1-13.
Solution 15: A polyurethane adhesive tape, including a substrate and the polyurethane adhesive according to solution 14 disposed on the substrate.
Solution 16: The polyurethane adhesive tape according to solution 15, wherein the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, release paper, or a release film.
Solution 17: A method for preparing a polyurethane adhesive tape, including the following steps: disposing the polyurethane adhesive composition according to any one of solutions 1-13 on a substrate; and curing the polyurethane adhesive composition. Though the above specific embodiments comprise a great many concrete details for the purpose of illustration through examples, it is to be understood by those of ordinary skill in the art that, many variations, modifications, replacements, and changes to these details shall all fall within the scope of the present invention as claimed in the claims. Therefore, the disclosure as described in the specific embodiments does not pose any limitation to the present invention as claimed in the claims. The proper scope of the present invention should be defined by the claims and proper legal equivalents thereof. All references referred to are incorporated herein by reference in their entireties.

Claims

What is claimed is:
1. A polyurethane adhesive composition, comprising: a) a polydiol, at least comprising a polyester diol having a weight average molecular weight of 400-4000; b) an aliphatic polycaprolactone triol having a weight average molecular weight of 100-600; and c) a polydiisocyanate, at least comprising one of a hexamethylene diisocyanate trimer and an isophorone diisocyanate trimer.
2. The polyurethane adhesive composition according to claim 1, wherein the polyester diol at least comprises one of an aromatic polyester diol and a fatty acid based polyester diol.
3. The polyurethane adhesive composition according to claim 1, wherein the polyester diol has a weight average molecular weight of 500-3000.
4. The polyurethane adhesive composition according to claim 1, wherein the aliphatic polycaprolactone triol has a weight average molecular weight of 200-400.
5. The polyurethane adhesive composition according to claim 1, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01-1:0.7.
6. The polyurethane adhesive composition according to claim 1, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.04-1:0.5.
7. The polyurethane adhesive composition according to claim 1, wherein the polydiol further comprises a dimer diol.
8. The polyurethane adhesive composition according to claim 7, wherein the weight ratio of the polyester diol to the dimer diol is 1 :0.1-1 : 1.
9. The polyurethane adhesive composition according to claim 7, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.04-1:0.3, and the weight ratio of the polyester diol to the dimer diol is 1 : 0.1 - 1 : 1.
10. The polyurethane adhesive composition according to claim 1, wherein the polyurethane adhesive composition further comprises d) silica particles.
11. The polyurethane adhesive composition according to claim 10, wherein the average particle size of the silica particles is 5-15 pm.
12. The polyurethane adhesive composition according to claim 10, wherein the silica particles at least comprise one of polydimethylsiloxane surface-modified silica particles, wax surface-modified silica particles, and surface-unmodified silica particles.
13. The polyurethane adhesive composition according to claim 10, wherein the ratio of the weight of the silica particles to the total weight of the polydiol, aliphatic polycaprolactone triol, and polydiisocyanate is 1: 100-5.1: 100.
14. A polyurethane adhesive, comprising a cured product of the polyurethane adhesive composition according to any one of claims 1-13.
15. A polyurethane adhesive tape, comprising a substrate and the polyurethane adhesive according to claim 14 disposed on the substrate.
16. The polyurethane adhesive tape according to claim 15, wherein the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, release paper, or a release film.
17. A method for preparing a polyurethane adhesive tape, comprising the following steps: disposing the polyurethane adhesive composition according to any one of claims 1-13 on a substrate; and curing the polyurethane adhesive composition.
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