CN113861919A - Polyurethane adhesive composition, polyurethane adhesive tape and method for producing polyurethane adhesive tape - Google Patents

Polyurethane adhesive composition, polyurethane adhesive tape and method for producing polyurethane adhesive tape Download PDF

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Publication number
CN113861919A
CN113861919A CN202010611843.0A CN202010611843A CN113861919A CN 113861919 A CN113861919 A CN 113861919A CN 202010611843 A CN202010611843 A CN 202010611843A CN 113861919 A CN113861919 A CN 113861919A
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polyurethane adhesive
adhesive composition
weight
substrate
silica particles
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Inventor
陈雪花
殷冠南
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to CN202010611843.0A priority Critical patent/CN113861919A/en
Priority to PCT/IB2021/055879 priority patent/WO2022003602A1/en
Publication of CN113861919A publication Critical patent/CN113861919A/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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a polyurethane adhesive composition, comprising: a) the polyglycol at least comprises polyester dihydric alcohol, and the weight average molecular weight of the polyester dihydric alcohol is 400-4000; b) the aliphatic polycaprolactone triol is characterized by comprising aliphatic polycaprolactone triol, wherein the weight average molecular weight of the aliphatic polycaprolactone triol is 100-600; and c) a polyisocyanate comprising at least one of hexamethylene diisocyanate trimer and isophorone diisocyanate trimer. Both the polyurethane adhesive prepared from the polyurethane adhesive composition provided according to the present invention and the polyurethane adhesive tape comprising the polyurethane adhesive have at least good room temperature adhesion properties and good high temperature resistance properties.

Description

Polyurethane adhesive composition, polyurethane adhesive tape and method for producing polyurethane adhesive tape
Technical Field
The invention relates to the field of adhesives, in particular to a polyurethane adhesive composition, a polyurethane adhesive, an adhesive tape comprising the polyurethane adhesive and a method for preparing the adhesive tape.
Background
With the advent and rapid development of technologies such as electric vehicles, sensors, VR/AR (virtual reality/augmented reality), internet of things, blockchains, and 5G, the chip market is growing rapidly. In chip manufacturing, a protective film is often required to protect the chip. For example, in the chip thinning process, a protective film is required to protect the chip; for another example, in some chip manufacturing processes involving high temperature (e.g., deposition of solder balls and copper pillars), a protective film is also required to protect the chip at a temperature above 200 ℃ (even above 260 ℃) for several minutes to tens of minutes. Therefore, it is required to provide a protective film having good room temperature adhesion properties and good high temperature resistance properties to meet this demand.
In addition, the deposition of high performance coatings can be used to improve the optical properties of the glass screen during the manufacture of the display. In order to be able to keep such coatings smooth on the atomic scale, it is necessary to prepare such coatings by means of a vapour deposition process. Generally, in a vapor deposition process (which generally has to be deposited at 200 ℃ or above 200 ℃), a protective film is required to protect the glass screen in the areas where no coating needs to be deposited; moreover, in the vapor deposition process, the protective film has to have good adhesion to the substrate so as not to blister, not to warp, and not to fall off; in addition, after the vapor deposition process is finished, the protective film must be easily removed without leaving residual glue on the substrate. Therefore, it is required to provide a protective film having good room temperature adhesion properties and good high temperature resistance properties to meet this demand.
Disclosure of Invention
One of the objects of the present invention is to provide a polyurethane adhesive composition and a polyurethane adhesive based on the composition. The polyurethane adhesive has at least good room temperature adhesion and good high temperature resistance, so that it can be used to solve at least some problems in the process of manufacturing chips or display glass screens.
Another object of the present invention is to provide a polyurethane adhesive tape.
It is still another object of the present invention to provide a method for preparing a polyurethane adhesive tape.
To this end, in one aspect, the present invention provides a polyurethane adhesive composition comprising: a) the polyglycol at least comprises polyester dihydric alcohol, and the weight average molecular weight of the polyester dihydric alcohol is 400-4000; b) the aliphatic polycaprolactone triol is characterized by comprising aliphatic polycaprolactone triol, wherein the weight average molecular weight of the aliphatic polycaprolactone triol is 100-600; and c) a polyisocyanate comprising at least one of hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.
According to some embodiments of the present invention, the polyester diol includes at least one of an aromatic polyester diol and a fatty acid polyester diol.
According to some technical schemes of the invention, the weight average molecular weight of the polyester diol is 500-3000.
According to some technical schemes of the invention, the weight average molecular weight of the aliphatic polycaprolactone triol is 200-400.
According to some technical schemes of the 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, and particularly preferably 1: 0.06-1: 0.3.
According to some aspects of the invention, the polyglycol further comprises: a dimer diol.
According to some embodiments of the present invention, the weight ratio of the polyester diol to the dimer diol is 1:0.1 to 1: 1.
According to some technical schemes of the invention, the weight ratio of the polyester dihydric alcohol to the aliphatic polycaprolactone trihydric alcohol is 1: 0.04-1: 0.3, and the weight ratio of the polyester dihydric alcohol to the dimer dihydric alcohol is 1: 0.1-1: 1; preferably, the weight ratio of the polyester dihydric alcohol to the aliphatic polycaprolactone trihydric alcohol is 1: 0.06-1: 0.3, and the weight ratio of the polyester dihydric alcohol to the dimer dihydric alcohol is 1: 0.1-1: 1.
According to some embodiments of the invention, the polyurethane adhesive composition further comprises: d) silica particles.
According to some embodiments of the present invention, the silica particles have an average particle diameter (D50) of 5 to 15 μm, preferably 6 to 10 μm.
According to some aspects of the present disclosure, the silica particles include at least one of Polydimethylsiloxane (PDMS) surface-modified silica particles, wax surface-modified silica particles, and surface-unmodified silica particles.
According to some technical schemes of the invention, the weight ratio of the silica particles to the total weight of the polydiol, the aliphatic polycaprolactone triol and the polyisocyanate is 1.0: 100-5.1: 100.
In yet another aspect, the present invention provides a polyurethane adhesive comprising: cured polyurethane adhesive compositions provided according to the present invention.
In another aspect, the present invention provides an adhesive tape comprising a substrate and a polyurethane adhesive provided according to the present invention disposed on the substrate.
According to some embodiments of the present invention, the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, a release paper, or a release film.
In still another aspect, the present invention provides a method of preparing a polyurethane adhesive tape, comprising the steps of: disposing a polyurethane adhesive composition provided according to the present invention onto a substrate; and, curing the polyurethane adhesive composition.
Hereinafter, the present invention will be described in more detail with reference to specific embodiments thereof.
Detailed Description
In the following, for the purpose of more clearly explaining the present invention, several technical solutions of the present invention and several technical solutions for comparison are explained. However, this section merely illustrates some embodiments which are claimed, wherein one or more of the technical features described in the technical aspects can be combined with any one or more of the technical aspects, and the technical features combined are also within the protection scope of the present application as long as the technical features do not depart from the spirit of the present invention.
As used herein, "good room temperature adhesion properties" means: the polyurethane adhesive or polyurethane adhesive tape can be adhered to the surface of a substrate (including, but not limited to, a glass substrate, a stainless steel substrate, or a silicon wafer substrate) under room temperature (23 ℃) conditions and has good room temperature 180 ° peel force on the substrate.
As used herein, "good high temperature resistance" means: after the high-temperature process, the polyurethane adhesive or the polyurethane adhesive tape can still be adhered to the substrate, has no bubbles and no falling off, can be completely removed from the surface of the protected substrate, and does not leave residual glue.
As used herein, "average particle size" means: the cumulative frequency (G or R) of the particle size distribution is equal to 50% of the particle size of the particles, also known as median diameter, also known as D50.
Polyurethane adhesive composition
The polyurethane adhesive composition provided by the invention comprises: a) the polyglycol at least comprises polyester dihydric alcohol, and the weight average molecular weight of the polyester dihydric alcohol is 400-4000; b) the aliphatic polycaprolactone triol is characterized by comprising aliphatic polycaprolactone triol, wherein the weight average molecular weight of the aliphatic polycaprolactone triol is 100-600; and c) a polyisocyanate comprising at least one of hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.
In the present invention, the polyester diol refers to a polyester polyol having a hydroxyl functionality of 2 obtained by a polycondensation reaction of a dicarboxylic acid with a diol or the like. The molecular weight of the polyester diol is 400-4000, preferably 500-3000. The polyester diol can adjust the polarity and cohesive strength of the polyurethane adhesive, thereby adjusting the room-temperature adhesion performance and high-temperature resistance of the polyurethane adhesive.
According to an embodiment of the present invention, the polyester diol may be fatty acid polyester diol (fat acid based polyester diol). The fatty acid polyester diol may be selected from Priplast 3162, Priplast 3172, Priplast 3192, or Priplast 3190 from Dacron Chemicals (Shanghai) Co., Ltd., Shanghai, China.
According to one embodiment of the invention, the polyester diol may also be an aromatic polyester diol. The aromatic polyester diol may be selected from XCPA-110 or XCPA-195, available from Asahi Chuan chemical Co., Ltd, Suzhou, China.
According to an embodiment of the present invention, the polyglycol may further include: dimer diols. The dimer diol may be prepared by hydrogenation reduction of dimer acid (dimer acid), wherein the dimer acid may be a complex mixture of dimer of C18 unsaturated fatty acid and higher oligomers with different structures. The dimer diol can adjust the polarity and the cohesive force of the polyurethane adhesive, thereby adjusting the room-temperature adhesion performance and the high-temperature resistance of the polyurethane adhesive.
According to an embodiment of the present invention, the dimer diol may be selected from Pripol 2033 or Pripol 2030, which are available from the procollagen (shanghai) ltd, located in shanghai, china.
According to one embodiment of the invention, the weight ratio of the polyester diol to the dimer diol is 1:0.1 to 1: 1. When the weight ratio of the polyester dihydric alcohol to the dimer dihydric alcohol is 1: 0.1-1: 1, the polyurethane adhesive has good high-temperature resistance.
In the invention, the aliphatic polycaprolactone triol is polyester polyol with a hydroxyl functionality of 3 formed by ring-opening polymerization of caprolactone, and the weight average molecular weight of the aliphatic polycaprolactone triol is 100-600, preferably 200-400. The aliphatic polycaprolactone triol can increase the crosslinking degree of the polyurethane adhesive, so that the high temperature resistance of the polyurethane adhesive is improved.
According to one embodiment of the invention, the aliphatic polycaprolactone triol may be selected from Capa 3050 or Capa 3031 available from Perstorp UK Ltd. of Cheshire, UK.
According to one embodiment of the invention, the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01 to 1:0.7, preferably 1:0.04 to 1: 0.5. When the weight ratio of the polyester dihydric alcohol to the aliphatic polycaprolactone trihydric alcohol is 1: 0.01-1: 0.7, the polyurethane adhesive can have good high-temperature resistance.
According to an embodiment of the present invention, the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01 to 1:0.7, preferably 1:0.04 to 1:0.5, and the weight ratio of the polyester diol to the dimer diol is 1:0.1 to 1:1, so that the polyurethane adhesive has good high temperature resistance.
In the present invention, the polyisocyanate includes at least one of hexamethylene diisocyanate trimer and isophorone diisocyanate trimer. Both the hexamethylene diisocyanate trimer and the isophorone diisocyanate trimer can provide good room-temperature adhesion performance and high-temperature resistance performance for the polyurethane adhesive.
According to one embodiment of the present invention, the hexamethylene diisocyanate trimer may be selected from N3800, N3390, or N3300 available from korsa, located in shanghai, china.
According to one embodiment of the present invention, the isophorone diisocyanate trimer can be selected from Z4470, which is available from korsa, located in shanghai, china.
According to one embodiment of the present invention, the polyurethane adhesive composition provided by the present invention may further comprise silica particles. In the present invention, the silica particles have an average particle diameter D50 of 5 to 15 μm, preferably 6 to 10 μm. The silicon dioxide 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 invention, the silica particles may be selected from one or more of the following group: 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 selected from acemantt 3300 available from winning companies located in shanghai city, china. According to one embodiment of the present invention, the wax surface-modified silica particles may be selected from OK520 available from winning companies located in shanghai city, china. According to one embodiment of the present invention, the surface-unmodified silica particles may be selected from TS-100 available from winning companies located in Shanghai City of China.
According to one embodiment of the invention, in the polyurethane adhesive composition provided by the invention, the ratio of the weight of the silica particles to the total weight of the polydiol, the aliphatic polycaprolactone triol and the polyisocyanate is 1.0: 100-5.1: 100. The ratio (A/B) can be calculated according to the following formula:
a is the weight of the silica particles,
b is the weight of the polyglycol plus the weight of the aliphatic polycaprolactone triol plus the weight of the polydiisocyanate,
a/B ═ weight (silica particles)/(weight of polyglycol + weight of aliphatic polycaprolactone triol + weight of polyisocyanate);
wherein, the weight of the polyglycol, the weight of the aliphatic polycaprolactone triol and the weight of the polyisocyanate can be respectively calculated according to the following formulas:
the weight of the polyglycol is the weight of the polyglycol solution x the solid content of the polyglycol solution,
the weight of the aliphatic polycaprolactone trihydric alcohol is equal to the weight of the aliphatic polycaprolactone trihydric alcohol solution multiplied by the solid content of the aliphatic polycaprolactone trihydric alcohol solution,
the weight of the polyisocyanate ═ the weight of the polyisocyanate solution × the solid content of the polyisocyanate solution.
Polyurethane adhesive
The polyurethane adhesive provided by the invention comprises: cured polyurethane adhesive compositions provided according to the present invention.
The components included in the polyurethane adhesive composition are described in the section of polyurethane adhesive composition in the specification, and the description is omitted.
According to one embodiment of the invention, the polyurethane adhesive may be prepared according to the following steps:
firstly, adding all the components included in the polyurethane adhesive composition into a suitable container at room temperature and mixing;
and step two, putting all the components of the mixed polyurethane adhesive composition into an oven for reaction and curing to obtain the polyurethane adhesive.
According to an embodiment of the present invention, in the second step, after the components of the mixed polyurethane adhesive composition are put into an oven, the temperature is raised from 120 ℃ to 150 ℃ and kept for 20 minutes, so that the polyurethane adhesive composition is reacted and cured to obtain the polyurethane adhesive.
According to an embodiment of the present invention, in the second step, after the components of the mixed polyurethane adhesive composition are put into the oven, the temperature is raised from 120 ℃ to 150 ℃ and maintained for 20 minutes, and then the temperature is lowered to 80 ℃ and maintained for 24 hours, so that the curing reaction is completed.
According to one embodiment of the present invention, in the first step, the components of the polyurethane adhesive composition except the silica particles may be added to a suitable container, and then the silica particles may be added to the container and dispersed at a high speed of 2500rpm for 5 to 15 minutes.
According to one embodiment of the invention, the polyurethane adhesive may be stored at room temperature.
According to one embodiment of the invention, the polyurethane adhesive provided by the invention has at least 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 appropriate amounts of a polyglycol, an aliphatic polycaprolactone triol, and a polyisocyanate, the polyurethane adhesive prepared from the polyurethane adhesive composition has good room temperature adhesion properties and good high temperature resistance properties 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 appropriate amounts of a polyglycol, an aliphatic polycaprolactone triol, a polydiisocyanate, and silica particles, the polyurethane adhesive prepared from the polyurethane adhesive composition has good room temperature adhesion properties and good high temperature resistance properties 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 appropriate amounts of a polyglycol, an aliphatic polycaprolactone triol, a polydiisocyanate, and silica particles, the polyurethane adhesive prepared from the polyurethane adhesive composition has good room temperature adhesion properties and good high temperature resistance properties on the surface of a stainless steel substrate.
Polyurethane adhesive tape
The adhesive tape (also referred to as a "protective film") provided by the invention comprises a substrate and the polyurethane adhesive provided by the invention arranged on the substrate. The polyurethane adhesive is described in the section of polyurethane adhesive in the specification, and the description is omitted.
According to one embodiment of the invention, the polyurethane adhesive may be disposed on at least one side of the substrate.
According to one embodiment of the invention, the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, a release paper, or a release film.
According to one embodiment of the present invention, the present invention provides an adhesive tape having at least good room temperature adhesion properties and good high temperature resistance properties.
According to one embodiment of the present invention, when the polyurethane adhesive composition provided by the present invention includes appropriate amounts of a polyglycol, an aliphatic polycaprolactone triol, and a polyisocyanate, a polyurethane adhesive tape prepared from the polyurethane adhesive composition has good room temperature adhesion properties and good high temperature resistance properties 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 appropriate amounts of a polyglycol, an aliphatic polycaprolactone triol, a polydiisocyanate, and silica particles, a polyurethane adhesive tape prepared from the polyurethane adhesive composition has good room temperature adhesion properties and good high temperature resistance properties 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 appropriate amounts of a polyglycol, an aliphatic polycaprolactone triol, a polydiisocyanate, and silica particles, a polyurethane adhesive tape prepared from the polyurethane adhesive composition has good room temperature adhesion properties and good high temperature resistance properties on a stainless steel substrate surface.
Method for preparing polyurethane adhesive tape
The method for preparing the polyurethane adhesive tape comprises the following steps: disposing the polyurethane adhesive composition provided by the present invention onto a substrate; and, curing the polyurethane adhesive composition.
The components included in the polyurethane adhesive composition are described in the section of polyurethane adhesive composition in the specification, and the description is omitted.
According to an embodiment of the present invention, specifically, the preparation method may include the steps of:
firstly, adding all the components included in the polyurethane adhesive composition into a suitable container at room temperature and mixing;
coating the mixed polyurethane adhesive composition on the surface of a base material; and
and step three, putting the base material coated with the polyurethane adhesive composition into an oven for reaction and curing to obtain the polyurethane adhesive tape.
According to an embodiment of the present invention, after the substrate coated with the polyurethane adhesive composition is placed in an oven, the temperature is raised from 120 ℃ to 150 ℃ and kept for 20 minutes to allow the polyurethane adhesive composition to react and cure, so as to obtain the polyurethane adhesive tape in step three.
According to an embodiment of the present invention, after the substrate coated with the polyurethane adhesive composition is placed in the oven, the temperature is raised from 120 ℃ to 150 ℃ and maintained for 20 minutes, and then the temperature is lowered to 80 ℃ and maintained for 24 hours in step three, so that the curing reaction is completed.
According to one embodiment of the present invention, in the first step, the components of the polyurethane adhesive composition except the silica particles may be added to a suitable container, and then the silica particles may be added to the container and dispersed at a high speed of 2500rpm for 5 to 15 minutes.
According to one embodiment of the present invention, the polyurethane adhesive tape may be stored at room temperature.
Examples
Hereinafter, preferred embodiments will be provided to better understand the present invention. However, the following examples are for illustrative purposes only and for the purpose of better understanding of the present invention by those skilled in the art, and the present invention should not be limited by these examples.
1. Raw materials
(1) Polyester diol
Priplast 3162 (abbreviated as "3162" in tables 1-1, 2-1, and 3-1, and having a solid content of 100% by weight), polyester diol, Secale Chemicals (Shanghai) Co., Ltd., Shanghai, China, molecular weight 1000.
Priplast 3172, (abbreviated as "3172" in tables 1-1, 2-1, and 3-1, and having a solid content of 100% wt) polyester diol, Secale Chemicals (Shanghai) Co., Ltd., Shanghai, China, molecular weight 3000.
Priplast 3192 (abbreviated as "3192" in tables 1-1, 2-1, and 3-1, and having a solid content of 100% by weight), polyester diol, Secale Chemicals (Shanghai) Co., Ltd., Shanghai, China, molecular weight 2000.
Priplast 3190 (abbreviated as "3190" in tables 1-1, 2-1, and 3-1, and having a solid content of 100% wt), polyester diol, Secale Chemicals (Shanghai) Co., Ltd., Shanghai, China, molecular weight 2000;
XCPA-110 (abbreviated as "110" in tables 1-1, 2-1, and 3-1, and having a solid content of 100% by weight), polyester diol, Asahi Sichuan chemical (Suzhou) Co., Ltd., Suzhou, China, having a molecular weight of 1000.
XCPA-195 (abbreviated as "195" in tables 1-1, 2-1, and 3-1, having a solid content of 100 wt%), polyester diol, Asahi Sichuan chemical (Suzhou) Co., Ltd., Suzhou, China, molecular weight 560.
XCP-1000N (abbreviated as "1000N" in tables 1-1, 2-1, and 3-1, and having a solid content of 100% by weight), polyester diol, Asahi Sichuan chemical (Suzhou) Co., Ltd., Suzhou, China, having a molecular weight of 1000.
XCP-500N (abbreviated as "500N" in tables 1-1, 2-1, and 3-1, and having a solid content of 100% by weight), polyester diol, Asahi Sichuan chemical (Suzhou) Co., Ltd., Suzhou, China, having a molecular weight of 500.
(2) Dimer diol
Pripol 2033 (abbreviated as "2033" in tables 1-1, 2-1, and 3-1, and having a solid content of 100% by weight), dimer diol, Secale Chemicals (Shanghai) Co., Ltd., located in Shanghai, China, and molecular weight of 570.
(3) Aliphatic polycaprolactone triols
Capa 3031 (abbreviated as "3031" in tables 1-1, 2-1, and 3-1, with 100% wt solids content), aliphatic polycaprolactone triol, Perstorp UK Ltd (Cheshire, UK.), molecular weight 300.
(4) Hexamethylene diisocyanate trimer
Desmodur N3800 (abbreviated as "N3800" in tables 1-1, 2-1 and 3-1, solid content 100% wt), Corcission Corp (located in Shanghai, China).
Desmodur N3390 (abbreviated as "N3390" in tables 1-1, 2-1 and 3-1, and having a solid content of 90% by weight), Corcission Corp (located in Shanghai, China).
(5) Isophorone diisocyanate trimer
Desmodur Z4470 (abbreviated as "Z4470" in tables 1-1, 2-1 and 3-1, with a solids content of 70% wt), Corcission Corp (located in Shanghai, China).
(6) Silica particles
TS-100, silica particles, winning company (located in shanghai, china), average diameter D50 ═ 6.5 μm.
Acemantt 3300, Polydimethylsiloxane (PDMS) surface modified silica particles, winning company (located in shanghai, china), average diameter D50 ═ 10 μm.
EXP 3400, Polydimethylsiloxane (PDMS) surface modified silica particles, winning company (located in shanghai, china), average diameter D50 ═ 6.5 μm.
OK-520, wax surface modified silica particles, winning company (located in shanghai, china), with an average diameter D50 of 6.5 μm.
(7) Base material
PI film (polyimide film), Ningbo Jinshan electronic materials Co., Ltd (Ningbo City, China).
(8) Others
MEK (methyl ethyl ketone), shanghai national drug company (located in shanghai city, china), analytical grade.
Dibutyl dilaurate (DBTDL, dibutyl tin dilaurate), shanghai national drug company (located in shanghai city, china).
Propylene glycol 1-monomethylether 2-acetate, Dow chemical company (located in Shanghai, China).
MIBK (methyl isobutyl ketone), shanghai national drug company (located in shanghai city, china), analytical grade.
BA (butyl acetate), shanghai national drug company (located in shanghai city, china), analytical grade.
Xylene, shanghai national drug company (located in shanghai city, china), analytical grade.
Acetyl acetone (acetylacetone), Shanghai national drug company (Shanghai, China), analytical grade.
2. Test method
(1) Room temperature adhesion test (Room temperature 180 degree Peel force test)
Cleaning a surface of a substrate (e.g., a glass substrate, a silicon wafer substrate, or a stainless steel substrate) with isopropyl alcohol (IPA) and blowing with compressed air to dry the surface of the substrate;
cutting a rectangular adhesive tape sample with the width of 1 inch;
the tape was laminated to the substrate surface using a self-moving roll (a roll press with self-moving rolls, commercially available from chem instruments, Fairfield, Ohio, USA) rolling back and forth once at a load of 4.5 lbf and a speed of 12 inches/minute;
the tape sample laminated to the substrate surface was left at room temperature (23 ℃) for 20 minutes, and then the room temperature 180 ° peel force of the tape sample on the substrate surface was measured at a rate of 12 inches/minute using an Instron (180 ° peel force tester, commercially available from Instron corporation, boston, usa) and the value of the room temperature 180 ° peel force measured was recorded.
(2) High temperature resistance test
Cleaning a surface of a substrate (e.g., a glass substrate, a silicon wafer substrate, or a stainless steel substrate) with isopropyl alcohol (IPA) and blowing with compressed air to dry the surface of the substrate;
cutting a rectangular adhesive tape sample with the width of 1 inch;
the tape was laminated to the substrate surface using a self-moving roll (a roll press with self-moving rolls, commercially available from chem instruments, Fairfield, Ohio, USA) rolling back and forth once at a load of 4.5 lbf and a speed of 12 inches/minute;
placing the substrate with the tape sample laminated thereon in a muffle furnace (commercially available from VULCAN 3-550 muffle furnace, Densky International, York, Pa., U.S.A.), raising the furnace temperature from room temperature to a predetermined temperature (e.g., 230 ℃ C., or 260 ℃ C.) at a rate of 35 ℃/minute, and holding at the predetermined temperature for a period of time (e.g., 10 minutes, 30 minutes, or 1 hour);
taking the substrate laminated with the adhesive tape sample out of the muffle furnace, cooling to room temperature, and observing whether the adhesive tape sample has blistering, bursting or falling off;
then manually pulling the adhesive tape sample from the laminated substrate to observe whether an adhesive remains on the surface of the substrate;
a tape sample is marked "good" if it neither bubbles, pops, or peels nor leaves adhesive residue on the substrate surface, otherwise it is marked "failed".
Example E1
1.00g of propylene glycol 1-monomethyl ether 2-acetate, 1.58g of Butyl Acetate (BA), 0.54g of methyl isobutyl ketone (MIBK), 0.98g of xylene, 1.77g of XCPA-110, 1.61g of XCPA-195, 0.40g of CAPA-3031, 0.15g of a 1 wt% MEK solution of DBTDL and 0.30g of acetylacetone were added to a 30ml plastic bottle, which was then capped and placed in a high speed mixer ARE-310 (commercially available from Thinky, Inc., Tokyo, Japan) and mixed for 2200 minutes at 2000 revolutions per minute and defoamed for 2 minutes at 2 revolutions per minute to give a homogeneous first solution;
then, 5.22g N3800 and 0.24g TS-100 were added to the first solution, and stirred for 5 minutes on a high speed disperser SFJ-400 (commercially available from Shanghai modern environmental engineering Co., Ltd., Shanghai, China) at 2500rpm to obtain a uniform second solution (i.e., a polyurethane adhesive solution). The ingredients and their contents contained in this second solution are shown in Table 1-1. For example, in this example, the molar ratio of NCO to OH is 1.034: 1; and the ratio of the weight of the silica particles to the total weight of the polyglycol, the aliphatic polycaprolactone triol and the polyisocyanate is 2.67:100, and the specific calculation formula of the ratio (A/B) is as follows:
a is the weight of the silica particles,
a/B ═ weight (silica particles)/(weight of polyglycol + weight of aliphatic polycaprolactone triol + weight of polyisocyanate);
wherein, the weight of the polyglycol, the weight of the aliphatic polycaprolactone triol and the weight of the polyisocyanate can be respectively calculated according to the following formulas:
the weight of polyglycol is the weight of polyglycol solution x the solids content of the weight of polyglycol,
the weight of the aliphatic polycaprolactone triol is equal to the weight of the aliphatic polycaprolactone triol solution multiplied by the solid content of the aliphatic polycaprolactone triol,
the weight of the polyisocyanate ═ the weight of the polyisocyanate solution × the solid content of the polyisocyanate solution;
in example 1, a/B is 0.24/(1.77 × 100% +1.61 × 100% +0.40 × 100% +5.22 × 100%) -2.67/100;
cutting the PI film with the thickness of 25 mu m into the size of A4 paper;
the second solution (i.e., the polyurethane adhesive solution) was coated on the PI film with a comma roller, placed in an oven, heated from 120 ℃ to 150 ℃, and kept at 150 ℃ for 20 minutes, allowed to dry and cure, thereby obtaining a polyurethane adhesive tape.
The polyurethane adhesive tape was subjected to a room temperature 180 ° peel force test (glass substrate surface) and a high temperature resistance test (glass substrate surface, 10 minutes at 260 ℃) in accordance with the test methods described herein, and the test results are shown in tables 1 to 2.
Examples E2 to E15
The polyurethane adhesive tapes of examples E2-E15 were prepared in the same manner as in example E1, except that the selection of the components and contents of the polyurethane adhesive composition used to prepare the polyurethane adhesive tapes was different, or the thickness of the polyurethane adhesive was different, as specifically listed in tables 1-1 and 1-2.
The polyurethane adhesive tapes of examples E2-E15 were subjected to the room temperature 180 peel force test (glass substrate surface) and the high temperature resistance test (glass substrate surface, 10 minutes at 260 ℃) in accordance with the test methods described herein, and the test results are shown in tables 1-2.
TABLE 1-1
Figure BDA0002562347010000141
Figure BDA0002562347010000151
Note 1: A/B ═ weight (silica particles)/(polyglycol weight + aliphatic polycaprolactone triol weight + polyisocyanate weight)
Tables 1 to 2
Figure BDA0002562347010000152
According to examples E1-E15, when the polyurethane adhesive composition provided by the present invention includes appropriate amounts of a polyglycol, an aliphatic polycaprolactone triol, and a polyisocyanate, the tape prepared therefrom has not only good adhesion to the glass surface at normal temperature, but also good high temperature resistance (neither bubbles, cracks, or drops nor adhesive residue on the surface of the glass substrate after 10 minutes at 260 ℃).
Example E16
61.63g MEK (methyl ethyl ketone), 24.17g XCPA-110, 24.17g XCPA-195,6.36g CAPA-3031, and 2.27g of a 1 wt% DBTDL solution in MEK were added to a 500ml plastic container and mixed well to obtain a uniform first solution;
then, 78.30g N3800 and 2.78g of Acematt 3300 were added to the first solution, and stirred on a high speed disperser SFJ-400 (commercially available from Shanghai modern environmental engineering Co., Ltd.) at 2500rpm for 5 minutes to obtain a uniform second solution (i.e., a polyurethane adhesive solution). The ingredients and their contents contained in this second solution are shown in Table 2-1. For example, in this example, the molar ratio of NCO to OH is 1.034: 1; and, a/B is 2.09/100;
cutting the PI film with the thickness of 25 mu m into the size of A4 paper;
the second solution (i.e., the polyurethane adhesive solution) was coated on the PI film with a comma roller, placed in an oven, heated from 120 ℃ to 150 ℃, allowed to dry and cure, and kept at 150 ℃ for 20 minutes, thereby obtaining a polyurethane adhesive tape.
The polyurethane adhesive tape was subjected to a room temperature 180 ° peel force test (silicon wafer substrate surface) and a high temperature resistance test (silicon wafer substrate surface) according to the test methods described herein, and the test results are shown in tables 2 to 2.
Examples E17-E23 and comparative example C1
The polyurethane adhesive tapes of examples E17-E23 and comparative example C1 were prepared in the same manner as in example E16, except that the selection of the components and contents of the polyurethane adhesive composition used to prepare the polyurethane adhesive tape, or the thickness of the polyurethane adhesive was different, as specifically listed in tables 2-1 and 2-2.
The polyurethane adhesive tapes of examples E17-E23 and comparative example C1 were subjected to a room temperature 180 ℃ peel force test (silicon wafer substrate surface) and a high temperature resistance test (silicon wafer substrate surface) according to the test methods described herein, and the test results are shown in tables 2-2.
TABLE 2-1
Figure BDA0002562347010000171
Note 2: A/B ═ weight (silica particles)/(polyglycol weight + aliphatic polycaprolactone triol weight + polyisocyanate weight)
Tables 2 to 2
Figure BDA0002562347010000172
Figure BDA0002562347010000181
According to examples E16-E23, when the polyurethane adhesive composition provided by the present invention includes appropriate amounts of a polyglycol, an aliphatic polycaprolactone triol, a polyisocyanate, and silica particles, the adhesive tape prepared therefrom has not only good adhesion to a silicon wafer substrate at normal temperature but also good high temperature resistance (it still has good adhesion to the silicon wafer substrate surface after 60 minutes at 230 ℃, and neither bubbles, cracks, or shedding have occurred nor adhesive residues remain on the silicon wafer substrate surface).
Comparative example C1, which did not include silica particles in the polyurethane adhesive composition, the polyurethane adhesive and tape prepared therefrom failed the high temperature resistance test.
Example E24
A500 ml plastic container was charged with 46.18g MEK (methyl ethyl ketone), 18.09g Priplast 3162, 18.09g Pripol 2033, 4.76g CAPA-3031, and 1.70g of a 1 wt% solution of DBTDL in MEK, and mixed well to give a uniform first solution;
58.16g N3800 and 2.02g of Acematt 3300 were then added to the first solution and stirred on a high speed disperser SFJ-400 (commercially available from Shanghai modern environmental engineering technology, Inc.) at 2500rpm for 5 minutes to obtain a homogeneous second solution (i.e., a polyurethane adhesive solution); the second solution contained the ingredients and their contents as shown in table 3-1, for example, in this example, the molar ratio of NCO to OH was 1.034:1, and a/B was 2.04/100;
cutting the PI film with the thickness of 25 mu m into the size of A4 paper;
the second solution (i.e., the polyurethane adhesive solution) was coated on the PI film with a comma roller, placed in an oven, heated from 120 ℃ to 150 ℃, allowed to dry and cure, and kept at 150 ℃ for 20 minutes, thereby obtaining a polyurethane adhesive tape.
The polyurethane adhesive tape was subjected to a room temperature 180 ° peel force test (stainless steel substrate surface) and a high temperature resistance test (stainless steel substrate surface 260 ℃/1hr) according to the test methods described herein, and the test results are shown in tables 3 to 2.
Examples E25-E32 and comparative example C2
The polyurethane adhesive tapes of examples E25-E32 and comparative example C2 were prepared in the same manner as in example E24, except that the selection of the components and contents of the polyurethane adhesive composition used to prepare the polyurethane adhesive tape, or the thickness of the polyurethane adhesive was different, as specifically listed in tables 3-1 and 3-2.
The polyurethane adhesive tapes of examples E25-E32 and comparative example C2 were tested for room temperature 180 peel force (stainless steel substrate surface) and high temperature resistance (stainless steel substrate surface 260C/1hr) according to the test methods described herein, and the test results are shown in tables 3-2.
TABLE 3-1
Figure BDA0002562347010000191
Note 3: A/B ═ weight (silica particles)/(polyglycol weight + aliphatic polycaprolactone triol weight + polyisocyanate weight)
TABLE 3-2
Figure BDA0002562347010000201
According to examples E24-E32, when the polyurethane adhesive composition provided by the present invention includes appropriate amounts of a polyglycol, an aliphatic polycaprolactone triol, and a polyisocyanate and silica particles, the polyurethane adhesive tape prepared from the polyurethane adhesive composition provided by the present invention has not only good adhesion to the surface of a stainless steel substrate at normal temperature but also good high temperature resistance (after 1 hour at 260 ℃, it still has good adhesion to the surface of a stainless steel substrate, and it neither develops blistering, bursting, or peeling nor leaves adhesive residue on the surface of a stainless steel substrate).
Comparative example C2, in which the polyurethane adhesive composition contained only polyester diol but not aliphatic polycaprolactone triol, the polyurethane adhesive and tape prepared therefrom failed the high temperature resistance test.
In conclusion, the polyurethane adhesive prepared from the polyurethane adhesive composition provided by the invention at least has good low-temperature adhesion performance and good high-temperature resistance.
According to the concept of the invention, the inventor at least provides the following technical scheme:
scheme 1. a polyurethane adhesive composition comprising: a) the polyglycol at least comprises polyester dihydric alcohol, and the weight average molecular weight of the polyester dihydric alcohol is 400-4000; b) the aliphatic polycaprolactone triol is characterized by comprising aliphatic polycaprolactone triol, wherein the weight average molecular weight of the aliphatic polycaprolactone triol is 100-600; and c) a polyisocyanate comprising at least one of hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.
Scheme 2. the polyurethane adhesive composition of scheme 1, wherein the polyester diol comprises at least one of an aromatic polyester diol and a fatty acid polyester diol.
Scheme 3. the polyurethane adhesive composition of scheme 1 or 2, wherein the polyester diol has a weight average molecular weight of 500-3000.
Scheme 4. the polyurethane adhesive composition according to any one of the preceding schemes, wherein the aliphatic polycaprolactone triol has a weight average molecular weight of 200-400.
Scheme 5. the polyurethane adhesive composition according to any one of the preceding schemes, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1: 0.01-1: 0.7.
Scheme 6. the polyurethane adhesive composition according to any one of the preceding schemes, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1: 0.04-1: 0.5.
Scheme 7. the polyurethane adhesive composition of any of the preceding schemes, wherein the polyglycol further comprises: a dimer diol.
Scheme 8 the polyurethane adhesive composition of scheme 7, wherein the weight ratio of the polyester diol to the dimer diol is 1:0.1 to 1: 1.
Scheme 9. the polyurethane adhesive composition according to scheme 7 or 8, 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.
The polyurethane adhesive composition of any of the preceding aspects, wherein the polyurethane adhesive composition further comprises: d) silica particles.
Scheme 11. the polyurethane adhesive composition according to scheme 10, wherein the silica particles have an average particle size of 5 to 15 μm.
Scheme 12. the polyurethane adhesive composition of scheme 10 or 11, wherein the silica particles comprise at least one of polydimethylsiloxane surface-modified silica particles, wax surface-modified silica particles, and surface-unmodified silica particles.
Scheme 13. the polyurethane adhesive composition according to scheme 10, 11 or 12, wherein the ratio of the weight of silica to the total weight of the polyglycol, the aliphatic polycaprolactone triol and the polyisocyanate is 1.0:100 to 5.1: 100.
Scheme 14. a polyurethane adhesive comprising: the cured polyurethane adhesive composition of any of embodiments 1-13.
Scheme 15. a polyurethane adhesive tape comprising a substrate and the polyurethane adhesive of scheme 14 disposed on the substrate.
Scheme 16. the polyurethane adhesive tape of scheme 15, wherein the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, a release paper, or a release film.
Scheme 17. a method of preparing a polyurethane adhesive tape, comprising the steps of: disposing the polyurethane adhesive composition of any of embodiments 1-13 onto a substrate; and, curing the polyurethane adhesive composition.
Although the foregoing detailed description contains many specific details for purposes of illustration, it will be appreciated by those of ordinary skill in the art that numerous variations, modifications, substitutions and alterations to these details are within the scope of the invention as claimed. Therefore, the disclosure described in the detailed description does not impose any limitation on the invention as claimed. The proper scope of the invention should be determined by the appended claims and their proper legal equivalents. All cited references are incorporated herein by reference in their entirety.

Claims (17)

1. A polyurethane adhesive composition comprising:
a) the polyglycol at least comprises polyester dihydric alcohol, and the weight average molecular weight of the polyester dihydric alcohol is 400-4000;
b) the aliphatic polycaprolactone triol is characterized by comprising aliphatic polycaprolactone triol, wherein the weight average molecular weight of the aliphatic polycaprolactone triol is 100-600; and
c) a polymeric diisocyanate including at least one of hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.
2. The polyurethane adhesive composition of claim 1, wherein the polyester diol comprises at least one of an aromatic polyester diol and a fatty acid polyester diol.
3. The polyurethane adhesive composition of claim 1, wherein the polyester diol has a weight average molecular weight of 500 to 3000.
4. The polyurethane adhesive composition of claim 1, wherein the aliphatic polycaprolactone triol has a weight average molecular weight of 200 to 400.
5. The polyurethane adhesive composition of claim 1, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.01 to 1: 0.7.
6. The polyurethane adhesive composition of claim 1, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.04 to 1: 0.5.
7. The polyurethane adhesive composition of claim 1, wherein the polyglycol further comprises: a dimer diol.
8. The polyurethane adhesive composition of claim 7, wherein the weight ratio of the polyester diol to the dimer diol is from 1:0.1 to 1: 1.
9. The polyurethane adhesive composition of claim 7, wherein the weight ratio of the polyester diol to the aliphatic polycaprolactone triol is 1:0.04 to 1:0.3, and the weight ratio of the polyester diol to the dimer diol is 1:0.1 to 1: 1.
10. The polyurethane adhesive composition of claim 1, wherein the polyurethane adhesive composition further comprises: d) silica particles.
11. The polyurethane adhesive composition of claim 10, wherein the silica particles have an average particle size of 5 to 15 μm.
12. The polyurethane adhesive composition of claim 10, wherein the silica particles comprise at least one of polydimethylsiloxane surface-modified silica particles, wax surface-modified silica particles, and surface-unmodified silica particles.
13. The polyurethane adhesive composition of claim 10, wherein the weight ratio of the silica particles to the total weight of the polyglycol, the aliphatic polycaprolactone triol, and the polyisocyanate is 1:100 to 5.1: 100.
14. A polyurethane adhesive comprising: the polyurethane adhesive composition of any one of claims 1-13 being cured.
15. A polyurethane adhesive tape comprising a substrate and the polyurethane adhesive of claim 14 disposed on the substrate.
16. The polyurethane adhesive tape of claim 15, wherein the substrate is a polyimide substrate, a polyester substrate, a polyetheretherketone substrate, a release paper, or a release film.
17. A method of preparing a polyurethane adhesive tape, comprising the steps of:
disposing the polyurethane adhesive composition of any of claims 1-13 onto a substrate; and the number of the first and second electrodes,
curing the polyurethane adhesive composition.
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