WO2023103480A1 - High-performance polyurethane pressure-sensitive adhesive, preparation method therefor, and application thereof - Google Patents

High-performance polyurethane pressure-sensitive adhesive, preparation method therefor, and application thereof Download PDF

Info

Publication number
WO2023103480A1
WO2023103480A1 PCT/CN2022/116014 CN2022116014W WO2023103480A1 WO 2023103480 A1 WO2023103480 A1 WO 2023103480A1 CN 2022116014 W CN2022116014 W CN 2022116014W WO 2023103480 A1 WO2023103480 A1 WO 2023103480A1
Authority
WO
WIPO (PCT)
Prior art keywords
parts
sensitive adhesive
polyurethane pressure
diisocyanate
performance polyurethane
Prior art date
Application number
PCT/CN2022/116014
Other languages
French (fr)
Chinese (zh)
Inventor
武鹏
李莹
姚俊
王小波
刘鎏
李二威
姚小龙
梁立明
Original Assignee
襄阳三沃航天薄膜材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 襄阳三沃航天薄膜材料有限公司 filed Critical 襄阳三沃航天薄膜材料有限公司
Publication of WO2023103480A1 publication Critical patent/WO2023103480A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/48—Polyethers
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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

Definitions

  • the disclosure relates to the technical field of pressure-sensitive adhesives, in particular to a high-performance polyurethane pressure-sensitive adhesive and its preparation method and application.
  • pressure-sensitive adhesives are mainly solvent-based acrylic pressure-sensitive adhesives, which have poor wetting effect on adherends, and the peeling force is unstable under high temperature or high humidity conditions, and it is easy to leave glue, which cannot adapt to high temperature and high humidity environments. Therefore, it is necessary to develop a high-performance polyurethane pressure-sensitive adhesive with good wetting effect and adaptable to high-temperature and high-humidity environment.
  • the disclosure provides a high-performance polyurethane pressure-sensitive adhesive, which includes: 30-50 parts of polyether polyol, 4-10 parts of isocyanate, 0.05-0.2 part of catalyst, 0.4-2 parts of chain extender, and solvent 100-150 parts, 0.5-3 parts of antioxidant, 5-12 parts of silicone heat-resistant monomer, 1-3 parts of plasticizer and 0.5-2 parts of curing agent; the plasticizer is castor oil and its derivatives one or more combinations of them.
  • the plasticizer is one or more combinations of dehydrated castor oil, hydrogenated castor oil, castor oil fatty acid and castor oil fatty acid ester.
  • the polyether polyol is one or more combinations of polytetrahydrofuran ether glycol, polypropylene glycol, polyoxypropylene triol, glycerol polyether, and ethylenediamine polyether tetraol;
  • the isocyanates are toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate , one or more combinations of isophorone diisocyanate and methylcyclohexane diisocyanate.
  • the catalyst is a tin-based catalyst selected from dioctyltin oxide, dibutyltin dichloride, dibutyltin dibromide, dibutyltin dilaurate, dibutyltin di
  • tin-based catalyst selected from dioctyltin oxide, dibutyltin dichloride, dibutyltin dibromide, dibutyltin dilaurate, dibutyltin di
  • tin acetate dibutyl tin sulfide, tributyl tin trichloroacetate, tributyl tin sulfide and dibutyl tin dimaleate.
  • the chain extender is a diamine chain extender selected from ethylenediamine, 1,2-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine , 1,4-cyclohexanediamine, N-hydroxymethylaminoethylamine and one or more combinations of N-ethylaminoethylamine.
  • the antioxidant is antioxidant 1076;
  • the solvent is one or more of toluene, butyl acetate, acetone, cyclohexanone, propylene glycol monoethyl ether and ethylene glycol mono-n-propyl ether kind of combination.
  • the silicone heat-resistant monomer is polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane and polyetherpolysiloxane One or more combinations of copolymers.
  • the curing agent is toluene diisocyanate-trimethylolpropane adduct, chlorobenzene diisocyanate-trimethylolpropane adduct, hexamethylene diisocyanate-trimethylolpropane adduct, hexamethylene diisocyanate-trimethylolpropane adduct, One or more of methylolpropane adduct, isophorone diisocyanate-trimethylolpropane adduct, isocyanurate and biuret.
  • the present disclosure also provides a method for preparing a high-performance polyurethane pressure-sensitive adhesive according to any one of the above, comprising the steps of:
  • the present disclosure also provides an application of a high-performance polyurethane pressure-sensitive adhesive in a PET protective film according to any one of the above, wherein the polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of a 50-60 ⁇ m thick PET base film Put the PET base film in an oven at 80-100°C for 5-10 minutes until the glue surface is dry. Mature in an oven at 40-50°C for 5 days for later use.
  • the present disclosure also provides the use of a high-performance polyurethane pressure-sensitive adhesive according to any one of the above in electrical appliances, automobiles, liquid crystal panels, communication products, computers and consumer electronics products.
  • Some embodiments of the present disclosure provide a high-performance polyurethane pressure-sensitive adhesive, calculated in parts by weight, comprising: 30-50 parts of polyether polyol, 4-10 parts of isocyanate, 0.05-0.2 parts of catalyst, 0.4 parts of chain extender -2 parts, 100-150 parts of solvent, 0.5-3 parts of antioxidant, 5-12 parts of silicone heat-resistant monomer, 1-3 parts of plasticizer and 0.5-2 parts of curing agent; the plasticizer is One or more combinations of castor oil and its derivatives.
  • the polyether polyol can be, for example, 35-45 parts, 38-42 parts, or 40-50 parts by weight, such as 30 parts, 32 parts, 34 parts, 36 parts, 40 parts, 42 parts, Any value in 44, 46, 48 or 50 parts or an interval value between any two point values;
  • the isocyanate can be 5-9 parts, 6-8 parts or 7-7.5 parts by weight, such as Any value in 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts or an interval value between any two point values;
  • the catalyst can be 0.07-0.18 parts, 0.08-0.15 parts or 0.09-0.12 shares, such as any value of 0.05 shares, 0.07 shares, 0.09 shares, 0.1 shares, 0.12 shares, 0.14 shares, 0.16 shares, 0.18 shares or 0.2 shares or the interval value between any two point values; chain extension
  • the agent may be in the range of 0.5-0.18, 0.8-0.15 or 0.1-0.14 parts by weight, such as 0.5, 0.7, 0.9, 1.0, 1.2, 1.4,
  • the plasticizer is one or more combinations of dehydrated castor oil, hydrogenated castor oil, castor oil fatty acid and castor oil fatty acid ester.
  • the polyether polyol is one or more combinations of polytetrahydrofuran ether diol, polypropylene glycol, polyoxypropylene triol, glycerol polyether, and ethylenediamine polyether tetraol.
  • the isocyanate is toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate , one or more combinations of lysine diisocyanate, isophorone diisocyanate and methylcyclohexane diisocyanate.
  • the catalyst is a tin-based catalyst selected from dioctyltin oxide, dibutyltin dichloride, dibutyltin dibromide, dibutyltin dilaurate, dibutyltin diacetate , one or more combinations of dibutyltin sulfide, tributyltin trichloroacetate, tributyltin sulfide and dibutyltin dimaleate.
  • the chain extender is a diamine chain extender selected from ethylenediamine, 1,2-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, 1 , One or more combinations of 4-cyclohexanediamine, N-hydroxymethylaminoethylamine and N-ethylaminoethylamine.
  • the antioxidant is Antioxidant 1076.
  • the solvent is one or more combinations of toluene, butyl acetate, acetone, cyclohexanone, propylene glycol monoethyl ether, and ethylene glycol mono-n-propyl ether.
  • the silicone heat-resistant monomer is polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane, and polyether polysiloxane copolymer One or more combinations of them.
  • the curing agent is toluene diisocyanate-trimethylolpropane adduct, chlorobenzene diisocyanate-trimethylolpropane adduct, hexamethylene diisocyanate-trimethylolpropane one or more of phenylpropane adduct, isophorone diisocyanate-trimethylolpropane adduct, isocyanurate and biuret.
  • Some embodiments of the present disclosure also provide a method for preparing a high-performance polyurethane pressure-sensitive adhesive, comprising the steps of:
  • 70-80% (such as 71-79%, 72-78% or 74-76%) of polyether polyol, isocyanate and solvent parts by weight are sequentially added in the reaction kettle, after stirring evenly, under N 2 protection, heating to 35-55°C (such as 38-52°C, 40-48°C or 42-46°C), then slowly add the catalyst dropwise to the reaction solution, and heat to 70-90°C while stirring (such as 72-88°C, 75°C -85°C or 78-82°C), after the dropwise addition is completed, keep the reaction at 70-90°C (such as 72-88°C, 75-85°C or 78-82°C) for 3-6h (such as 3h, 4h, 5h or 6h) , to obtain the mixture A;
  • Some embodiments of the present disclosure also provide an application of a high-performance polyurethane pressure-sensitive adhesive in a PET protective film, the method is: uniformly coating the polyurethane pressure-sensitive adhesive -56 ⁇ m) thick PET base film on the corona surface, and put the PET base film in an oven at 80-100°C for 5-10min (such as 5min, 6min, 7min, 8min, 9min or 10min) until the glue surface is dry, control The thickness of the dry glue is 10 ⁇ 1 ⁇ m, and then cover the glue surface with a release film with a thickness of 50 ⁇ m, and place it in an oven at 40-50°C (such as 41-49°C, 42-48°C or 45-47°C) for curing 5d spare.
  • 5-10min such as 5min, 6min, 7min, 8min, 9min or 10min
  • the thickness of the dry glue is 10 ⁇ 1 ⁇ m, and then cover the glue surface with a release film with a thickness of 50 ⁇ m, and place it in an oven at 40-50°
  • Some embodiments of the present disclosure also provide a high-performance polyurethane pressure-sensitive adhesive as described above in electrical appliances (such as wire and cable joints and terminals, insulation protection of motor coils; such as refrigerators, washing machines and other electrical conduits or splints. Sealing), automobiles, liquid crystal panels, communication products (such as when circuit boards are wave soldered, the parts that are not tinned need to be masked, and masking tape is used when spraying), computers and consumer electronics (such as in ultra-miniature In electronic equipment, the use of pressure-sensitive adhesive tapes and hot-melt pressure-sensitive adhesives for leadless component packaging).
  • the disclosure proposes a high-performance polyurethane pressure-sensitive adhesive that has good wetting effect, is easy to peel off, has no residual glue pollution, and can adapt to high-temperature and high-humidity environments, and a preparation method thereof.
  • This disclosure introduces a special plasticizer in the preparation process of polyurethane pressure-sensitive adhesive.
  • the polyurethane pressure-sensitive adhesive has excellent Wetting performance (less than 10s), pollution resistance performance, and the pressure-sensitive adhesive prepared at the same time has stable peeling force and excellent heat resistance (180 ° C 2h glass plate without pollution), can be widely used in mobile phones, automobiles, High-end fields such as panel manufacturing.
  • a high-performance polyurethane pressure-sensitive adhesive calculated in parts by weight, comprising: polyether polyol: 10 parts of polytetrahydrofuran ether glycol, 20 parts of polypropylene glycol; isocyanate: 1 part of toluene diisocyanate, diphenylmethane-4, 3 parts of 4'-diisocyanate; catalyst: 0.02 part of dioctyltin oxide, 0.03 part of dibutyltin dichloride; chain extender: 0.2 part of ethylenediamine, 0.2 part of 1,2-propylenediamine; solvent: 40 parts of toluene, 60 parts of butyl acetate; antioxidant: 1076 0.5 parts of antioxidant; silicone heat-resistant monomer: 2 parts of polydimethylsiloxane, 3 parts of cyclomethicone; plasticizer : 0.5 part of dehydrated castor oil, 0.5 part of hydrogenated castor oil; curing agent: 0.2 part of toluene diisocyanate
  • a preparation method of high-performance polyurethane pressure-sensitive adhesive comprising the steps of:
  • the polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of the PET base film with a thickness of 50 ⁇ m, and the PET base film is baked in an oven at 80 ° C for 5 minutes to The glue surface was dried, and the thickness of the dry glue was controlled to be 9 ⁇ m, and then a release film with a thickness of 50 ⁇ m was covered on the glue surface, and it was placed in an oven at 40° C. for 5 d for later use.
  • a high-performance polyurethane pressure-sensitive adhesive calculated in parts by weight, comprising: 30 parts of polyoxypropylene triol, 20 parts of glycerol polyether; isocyanate: 2 parts of xylylene diisocyanate, tetramethylphthalylene 3 parts of hexamethylene diisocyanate, 5 parts of hexamethylene diisocyanate; catalyst: 0.5 part of dibutyltin dibromide, 0.6 part of dibutyltin dilaurate, 0.9 part of dibutyltin diacetate; chain extender: 1 part of 1,6-hexamethylenediamine, 1 part of isophorone diamine; solvent: 70 parts of acetone, 80 parts of cyclohexanone; antioxidant: 3 parts of antioxidant 1076; silicone heat-resistant sheet Body: 5 parts of aminosiloxane, 7 parts of polymethylphenylsiloxane; plasticizer: 1 part of castor oil fatty acid, 2 parts of castor oil fatty
  • a preparation method of high-performance polyurethane pressure-sensitive adhesive comprising the steps of:
  • the temperature of the mixed solution A is lowered to 60° C., and then sequentially add chain extender, plasticizer and 20% by weight of the solvent, and keep warm at 60° C. for 3 hours to obtain the mixed solution B;
  • a high-performance polyurethane pressure-sensitive adhesive in a PET protective film.
  • the polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of a 60 ⁇ m thick PET base film, and the PET base film is baked in an oven at 100°C for 10 minutes to The glue surface is dried, and the thickness of the dry glue is controlled to be 11 ⁇ m, and then a release film with a thickness of 50 ⁇ m is covered on the glue surface, and it is placed in an oven at 50° C. for 5 d for later use.
  • a high-performance polyurethane pressure-sensitive adhesive calculated in parts by weight, comprising: polyether polyol: 10 parts of glycerol polyether, 25 parts of ethylenediamine polyether tetraol; isocyanate: 1 part of lysine diisocyanate, isofor 2 parts of ketone diisocyanate, 2 parts of methyl cyclohexane diisocyanate; Catalyst: 0.3 parts of dibutyl tin sulfide, 0.3 parts of tributyl tin trichloroacetate, 0.3 parts of tributyl tin sulfide; Chain extender: 1, 0.2 parts of 4-cyclohexanediamine, 0.3 parts of N-hydroxymethylaminoethylamine, 0.2 parts of N-ethylaminoethylamine; solvent: 60 parts of propylene glycol monoethyl ether, 50 parts of ethylene glycol mono-n-propyl ether
  • a preparation method of high-performance polyurethane pressure-sensitive adhesive comprising the steps of:
  • the temperature of the mixed solution A is lowered to 45°C, and then sequentially add chain extender, plasticizer and 28% of the weight of the solvent, and keep warm at 45°C for 1.5h to obtain the mixed solution B;
  • the polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of the PET base film with a thickness of 55 ⁇ m, and the PET base film is baked in an oven at 85 ° C for 6 minutes to The glue surface is dried, and the thickness of the dry glue is controlled to be 10 ⁇ m, and then a release film with a thickness of 50 ⁇ m is covered on the glue surface, and it is placed in an oven at 45° C. for 5 d for later use.
  • a high-performance polyurethane pressure-sensitive adhesive calculated in parts by weight, comprising: polyether polyol: 15 parts of polytetrahydrofuran ether glycol, 15 parts of glycerol polyether, 15 parts of ethylenediamine polyether tetraol; isocyanate: diphenyl 2 parts of methyl methane-4,4'-diisocyanate, 2 parts of tetramethylxylylene diisocyanate, 2 parts of lysine diisocyanate; Catalyst: 0.04 parts of dioctyltin oxide, tributyl trichloroacetic acid 0.04 parts of tin, 0.04 parts of dibutyltin dimaleate; chain extender: 0.3 parts of 1,6-hexamethylenediamine, 0.3 parts of isophorone diamine, 0.4 parts of N-ethylaminoethylamine ; Solvent: 50 parts of toluene, 70 parts of acetone;
  • a preparation method of high-performance polyurethane pressure-sensitive adhesive comprising the steps of:
  • the temperature of the mixed solution A is lowered to 45°C, and then sequentially add chain extender, plasticizer and 25% of the weight of the solvent, and keep warm at 45°C for 1.5h to obtain the mixed solution B;
  • the polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of the PET base film with a thickness of 50 ⁇ m, and the PET base film is baked in an oven at 95 ° C for 8 minutes to The glue surface is dried, and the thickness of the dry glue is controlled to be 10 ⁇ m, and then a release film with a thickness of 50 ⁇ m is covered on the glue surface, and it is placed in an oven at 45° C. for 5 d for later use.
  • a high-performance polyurethane pressure-sensitive adhesive calculated in parts by weight, comprising: polyether polyol: 10 parts of polytetrahydrofuran ether glycol, 10 parts of polypropylene glycol, 20 parts of ethylenediamine polyether tetraol; isocyanate: diphenyl 2 parts of methane-4,4'-diisocyanate, 2 parts of isophorone diisocyanate, 3 parts of methylcyclohexane diisocyanate; catalyst: 0.05 parts of dibutyl tin dibromide, 0.05 parts of dibutyl tin sulfide , 0.05 part of tributyltin trichloroacetate; chain extender: 0.5 part of isophorone diamine, 0.5 part of 1,4-cyclohexanediamine, 0.5 part of N-ethylaminoethylamine; solvent: butyl acetate 60 parts of ester, 70 parts of cyclohexanone
  • a preparation method of high-performance polyurethane pressure-sensitive adhesive comprising the steps of:
  • the polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of the PET base film with a thickness of 60 ⁇ m, and the PET base film is baked in an oven at 100 ° C for 5 minutes to The glue surface is dried, and the thickness of the dry glue is controlled to be 11 ⁇ m, and then a release film with a thickness of 50 ⁇ m is covered on the glue surface, and it is placed in an oven at 50° C. for 5 d for later use.
  • a high-performance polyurethane pressure-sensitive adhesive calculated in parts by weight, comprising: polyether polyol: 10 parts of polytetrahydrofuran ether glycol, 14 parts of polyoxypropylene triol, 14 parts of ethylenediamine polyether tetraol; isocyanate: 2 parts of toluene diisocyanate, 2 parts of xylylene diisocyanate, 2 parts of hexamethylene diisocyanate, 3 parts of lysine diisocyanate; catalyst: 0.03 parts of dioctyltin oxide, tributyl trichloroacetic acid 0.04 parts of tin, 0.05 parts of tributyltin sulfide, 0.06 parts of dibutyltin dimaleate; chain extenders: 0.6 parts of 1,2-propanediamine, 0.3 parts of isophorone diamine, 0.3 parts of 1,4- 0.5 parts of cyclohexanediamine, 0.4 parts of N-hydroxymethyla
  • a preparation method of high-performance polyurethane pressure-sensitive adhesive comprising the steps of:
  • the temperature of the mixed solution A is lowered to 45°C, and then sequentially add chain extender, plasticizer and 27% of the weight of the solvent, and keep the temperature at 45°C for 1.5h to obtain the mixed solution B;
  • the polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of the PET base film with a thickness of 50 ⁇ m, and the PET base film is baked in an oven at 85 ° C for 5 minutes to The glue surface was dried, and the thickness of the dry glue was controlled to be 10 ⁇ m, and then a release film with a thickness of 50 ⁇ m was covered on the glue surface, and it was placed in an oven at 40° C. for 5 d for later use.
  • Example 1 lacking plasticizer as Comparative Example 1, the remaining components are the same as Example 1, and the preparation method and application are also the same.
  • Example 1 lacking silicone heat-resistant monomer as Comparative Example 2, the remaining components are the same as Example 1, and the preparation method and application are also the same.
  • Example 1 lacking a chain extender as Comparative Example 3, the remaining components are the same as Example 1, and the preparation method and application are also the same.
  • Example 1 lacking plasticizer, silicone heat-resistant monomer and chain extender as Comparative Example 4, the remaining components are the same as Example 1, and the preparation method and application are also the same.
  • the PET protective film coated with the polyurethane pressure-sensitive adhesive prepared in the above Examples 1-6 and Comparative Examples 1-4 was subjected to the following tests to detect the properties of the polyurethane pressure-sensitive adhesive.
  • the test method is as follows:
  • Peeling force test test according to GB 2792-1998 standard test method, stick the protective film with rubber surface on SU304 stainless steel plate, soak for 30min, test condition is 23 ⁇ 2°C, humidity is 65 ⁇ 5%, measure in 180° direction Peeling force to stainless steel plate, the unit is gf/25mm.
  • Peel force growth test In addition, test the peel force after cooling to room temperature in an oven at 120°C for 1 hour.
  • Heat resistance test Attach the cut PET protective film with a width of 25mm on the steel plate and glass respectively, put it in an oven and bake at 180°C for 2 hours, after cooling to room temperature, tear it off and see if there is any residue on the glass plate and steel plate glue.
  • Humidity and heat resistance test for glass Attach the prepared PET protective film on both sides of a clean glass cover, place it in an environment with a temperature of 85°C and a humidity of 85% for 15 days, and when the PET protective film is removed, observe the glass surface. No pollution (speckle shadow, residual glue, etc.).
  • Wettability test for glass Cut out a 100mm ⁇ 100mm PET protective film, attach it to the glass cover, and record the time until the protective film is completely wetted and attached to the glass cover until there are no bubbles. Evaluation criteria: excellent ( ⁇ 10s); good (10-20s); poor (>20s).
  • the polyurethane pressure-sensitive adhesive of the present disclosure has the advantages of good wettability, small increase in high-temperature peeling force, heat and humidity resistance, and no adhesive residue or speckle at 180°C for 2 hours.
  • the pressure-sensitive adhesive prepared at the same time has stable peeling force and excellent heat resistance; the introduction of a suitable chain extender can effectively improve the relative molecular weight of the polyurethane glue, improve the cohesion and initial adhesion of the pressure-sensitive adhesive, and effectively prevent residual glue. Appearance, improve the pollution resistance of pressure-sensitive adhesives, can be widely used in high-end fields such as mobile phones, automobiles, and panel manufacturing.
  • the disclosure provides a high-performance polyurethane pressure-sensitive adhesive.
  • the polyurethane pressure-sensitive adhesive has good wettability to the adherend, and the peeling force is still stable without increasing even under high temperature and/or high humidity conditions, and has strong pollution resistance. , can meet the use requirements in high-temperature scenes, and therefore has excellent industrial applicability.

Abstract

The present disclosure provides a high-performance polyurethane pressure-sensitive adhesive, a preparation method therefor, and an application thereof. The polyurethane pressure-sensitive adhesive comprises, in parts by weight, 30-50 parts of polyether polyol, 4-10 parts of isocyanate, 0.05-0.2 parts of a catalyst, 0.4-2 parts of a chain extender, 100-150 parts of a solvent, 0.5-3 parts of an antioxidant, 5-12 parts of a silicone heat-resistant monomer, 1-3 parts of a plasticizer, and 0.5-2 parts of a curing agent. The polyurethane pressure-sensitive adhesive of the present disclosure has good wettability to adherends, stable peeling force that does not increase even under high temperature and/or high humidity conditions, and strong contamination resistance, and can meet use requirements in high temperature scenarios.

Description

一种高性能聚氨酯压敏胶及其制备方法和应用A kind of high-performance polyurethane pressure-sensitive adhesive and its preparation method and application
相关申请的交叉引用Cross References to Related Applications
本公开要求于2021年12月07日提交中国专利局的申请号为CN202111483032.8、名称为“一种高性能聚氨酯压敏胶及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。This disclosure claims the priority of the Chinese patent application with application number CN202111483032.8 and titled "A high-performance polyurethane pressure-sensitive adhesive and its preparation method and application" submitted to the Chinese Patent Office on December 07, 2021, all of which The contents are incorporated by reference in this disclosure.
技术领域technical field
本公开涉及压敏胶技术领域，尤其涉及一种高性能聚氨酯压敏胶及其制备方法和应用。The disclosure relates to the technical field of pressure-sensitive adhesives, in particular to a high-performance polyurethane pressure-sensitive adhesive and its preparation method and application.
背景技术Background technique
压敏胶广泛用于办公、包装、电器、汽车、液晶面板及手机元器件的制备制造过程汇总。在电子、汽车等使用场景，压敏胶必须具备优异的内聚力和粘合力，既要保证在剥离被保护面时无残胶，无污染，又要保证容易剥离。尤其是在模切等高温使用场景下，对保护膜的性能要求更高。Pressure-sensitive adhesives are widely used in the preparation and manufacturing process of office, packaging, electrical appliances, automobiles, LCD panels and mobile phone components. In usage scenarios such as electronics and automobiles, pressure-sensitive adhesives must have excellent cohesion and adhesion. It is necessary to ensure that there is no adhesive residue and no pollution when peeling off the protected surface, and it must also be easy to peel off. Especially in high-temperature scenarios such as die-cutting, the performance requirements for the protective film are higher.
目前压敏胶主要以溶剂型丙烯酸酯压敏胶为主，对粘附物的润湿效果较差，剥离力在经过高温或高湿条件下不稳定，容易残胶，无法适应高温高湿环境，为此需要研发一种湿润效果好、能适应高温高湿环境的高性能聚氨酯压敏胶。At present, pressure-sensitive adhesives are mainly solvent-based acrylic pressure-sensitive adhesives, which have poor wetting effect on adherends, and the peeling force is unstable under high temperature or high humidity conditions, and it is easy to leave glue, which cannot adapt to high temperature and high humidity environments. Therefore, it is necessary to develop a high-performance polyurethane pressure-sensitive adhesive with good wetting effect and adaptable to high-temperature and high-humidity environment.
发明内容Contents of the invention
本公开提供一种高性能聚氨酯压敏胶，按照重量份数计算，包括：聚醚多元醇30-50份、异氰酸酯4-10份、催化剂0.05-0.2份、扩链剂0.4-2份、溶剂100-150份、抗氧剂0.5-3份、有机硅耐热单体5-12份、增塑剂1-3份和固化剂0.5-2份；所述增塑剂为蓖麻油及其衍生物中的一种或多种组合。The disclosure provides a high-performance polyurethane pressure-sensitive adhesive, which includes: 30-50 parts of polyether polyol, 4-10 parts of isocyanate, 0.05-0.2 part of catalyst, 0.4-2 parts of chain extender, and solvent 100-150 parts, 0.5-3 parts of antioxidant, 5-12 parts of silicone heat-resistant monomer, 1-3 parts of plasticizer and 0.5-2 parts of curing agent; the plasticizer is castor oil and its derivatives one or more combinations of them.
在一些实施方式中，所述增塑剂为脱水蓖麻油、氢化蓖麻油、蓖麻油脂肪酸和蓖麻油脂肪酸酯中的一种或多种组合。In some embodiments, the plasticizer is one or more combinations of dehydrated castor oil, hydrogenated castor oil, castor oil fatty acid and castor oil fatty acid ester.
在一些实施方式中，所述聚醚多元醇为聚四氢呋喃醚二醇、聚丙二醇、聚氧化丙烯三醇、甘油聚醚、乙二胺聚醚四醇中的一种或多种组合；所述异氰酸酯为甲苯二异氰酸酯、二苯基甲烷-4,4'-二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、异佛尔酮二异氰酸酯和甲基环已烷二异氰酸酯中的一种或多种组合。In some embodiments, the polyether polyol is one or more combinations of polytetrahydrofuran ether glycol, polypropylene glycol, polyoxypropylene triol, glycerol polyether, and ethylenediamine polyether tetraol; The isocyanates are toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate , one or more combinations of isophorone diisocyanate and methylcyclohexane diisocyanate.
在一些实施方式中，所述催化剂为锡系催化剂，选自二辛基氧化锡、二丁基二氯化锡、二丁基二溴化锡、二丁基二月桂酸锡、二丁基二乙酸锡、二丁基硫化锡、三丁基三氯乙酸锡、三丁基硫化锡和二丁基二马来酸锡中的一种或多种组合。In some embodiments, the catalyst is a tin-based catalyst selected from dioctyltin oxide, dibutyltin dichloride, dibutyltin dibromide, dibutyltin dilaurate, dibutyltin di One or more combinations of tin acetate, dibutyl tin sulfide, tributyl tin trichloroacetate, tributyl tin sulfide and dibutyl tin dimaleate.
在一些实施方式中，所述扩链剂为二元胺扩链剂，选自乙二胺、1,2-丙二胺、1,6-六亚甲基二胺、异氟尔酮二胺、1,4-环己烷二胺、N-羟甲基氨基乙胺和N-乙基氨基乙胺中的一种或多种组合。In some embodiments, the chain extender is a diamine chain extender selected from ethylenediamine, 1,2-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine , 1,4-cyclohexanediamine, N-hydroxymethylaminoethylamine and one or more combinations of N-ethylaminoethylamine.
在一些实施方式中，所述抗氧剂为抗氧剂1076；所述溶剂为甲苯、乙酸丁酯、丙酮、环己酮、丙二醇单***和乙二醇单正丙醚中的一种或多种组合。In some embodiments, the antioxidant is antioxidant 1076; the solvent is one or more of toluene, butyl acetate, acetone, cyclohexanone, propylene glycol monoethyl ether and ethylene glycol mono-n-propyl ether kind of combination.
在一些实施方式中，所述有机硅耐热单体为聚二甲基硅氧烷、环甲基硅氧烷、氨基硅氧烷、聚甲基苯基硅氧烷和聚醚聚硅氧烷共聚物中的一种或多种组合。In some embodiments, the silicone heat-resistant monomer is polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane and polyetherpolysiloxane One or more combinations of copolymers.
在一些实施方式中，所述固化剂为甲苯二异氰酸酯-三羟甲基丙烷加成物、氯苯二异氰酸-三羟甲基丙烷加成物、六亚甲基二异氰酸-三羟甲基丙烷加成物、异氟尔酮二异氰酸-三羟甲基丙烷加成物、异氰脲酸酯和缩二脲中的一种或多种。In some embodiments, the curing agent is toluene diisocyanate-trimethylolpropane adduct, chlorobenzene diisocyanate-trimethylolpropane adduct, hexamethylene diisocyanate-trimethylolpropane adduct, hexamethylene diisocyanate-trimethylolpropane adduct, One or more of methylolpropane adduct, isophorone diisocyanate-trimethylolpropane adduct, isocyanurate and biuret.
本公开还提供一种制备根据上文任一所述的一种高性能聚氨酯压敏胶的方法，包括如下步骤：The present disclosure also provides a method for preparing a high-performance polyurethane pressure-sensitive adhesive according to any one of the above, comprising the steps of:
S1，在反应釜中依次加入聚醚多元醇、异氰酸酯和溶剂重量份数的70-80％，搅拌均匀后在N 2保护下，将反应液加热至35-55℃，然后向反应液中缓慢滴加催化剂，边搅拌边加热至70-90℃，滴加完毕后70-90℃保温反应3-6h，得到混合液A； S1, add polyether polyol, isocyanate and 70-80% of the weight of the solvent in sequence in the reaction kettle, stir evenly, and under the protection of N2 , heat the reaction solution to 35-55°C, and then slowly add to the reaction solution Add the catalyst dropwise, and heat to 70-90°C while stirring. After the dropwise addition, keep the reaction at 70-90°C for 3-6h to obtain the mixed solution A;
S2，将混合液A的温度降至40-60℃，然后依次加入扩链剂、增塑剂和溶剂重量份数的20-30％，在40-60℃下保温反应1-3h，得到混合液B；S2, lower the temperature of the mixed liquid A to 40-60°C, then sequentially add chain extender, plasticizer and 20-30% by weight of the solvent, and keep warm at 40-60°C for 1-3h to obtain a mixed Liquid B;
S3，在40-60℃不断搅拌条件下，依次将耐热单体、抗氧剂和固化剂滴加到混合液B中，滴加完毕后搅拌10-30min，然后将反应液冷却至20-30℃，得到聚氨酯压敏胶。S3, under the condition of constant stirring at 40-60°C, add the heat-resistant monomer, antioxidant and curing agent dropwise to the mixed solution B in sequence, stir for 10-30min after the dropwise addition, and then cool the reaction solution to 20- 30°C to obtain a polyurethane pressure-sensitive adhesive.
本公开还提供一种根据上文任一所述的一种高性能聚氨酯压敏胶在PET保护膜中的应用，将聚氨酯压敏胶均匀涂覆在50-60μm厚的PET基膜电晕面上，并将PET基膜置于80-100℃烘箱中烘5-10min至胶面干燥，控制干胶厚度为10±1μm，然后在胶面上覆50μm厚度的离型膜，并将其置于40-50℃烘箱中熟化5d备用。The present disclosure also provides an application of a high-performance polyurethane pressure-sensitive adhesive in a PET protective film according to any one of the above, wherein the polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of a 50-60 μm thick PET base film Put the PET base film in an oven at 80-100°C for 5-10 minutes until the glue surface is dry. Mature in an oven at 40-50°C for 5 days for later use.
本公开还提供根据上文任一所述的一种高性能聚氨酯压敏胶在电器、汽车、液晶面板、通讯产品、计算机和消费电子产品中的用途。The present disclosure also provides the use of a high-performance polyurethane pressure-sensitive adhesive according to any one of the above in electrical appliances, automobiles, liquid crystal panels, communication products, computers and consumer electronics products.
具体实施方式Detailed ways
下面将结合本公开实施方式，对本公开实施方式中的技术方案进行清楚、完整地描述， 显然，所描述的实施方式仅仅是本公开一部分实施方式，而不是全部的实施方式。基于本公开中的实施方式，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，都属于本公开保护的范围。The technical solutions in the embodiments of the present disclosure will be clearly and completely described below in conjunction with the embodiments of the present disclosure. Obviously, the described embodiments are only part of the embodiments of the present disclosure, not all of them. Based on the implementation manners in the present disclosure, all other implementation manners obtained by persons of ordinary skill in the art without creative efforts shall fall within the protection scope of the present disclosure.
本公开的一些实施方式提供了一种高性能聚氨酯压敏胶，按照重量份数计算，包括：聚醚多元醇30-50份、异氰酸酯4-10份、催化剂0.05-0.2份、扩链剂0.4-2份、溶剂100-150份、抗氧剂0.5-3份、有机硅耐热单体5-12份、增塑剂1-3份和固化剂0.5-2份；所述增塑剂为蓖麻油及其衍生物中的一种或多种组合。Some embodiments of the present disclosure provide a high-performance polyurethane pressure-sensitive adhesive, calculated in parts by weight, comprising: 30-50 parts of polyether polyol, 4-10 parts of isocyanate, 0.05-0.2 parts of catalyst, 0.4 parts of chain extender -2 parts, 100-150 parts of solvent, 0.5-3 parts of antioxidant, 5-12 parts of silicone heat-resistant monomer, 1-3 parts of plasticizer and 0.5-2 parts of curing agent; the plasticizer is One or more combinations of castor oil and its derivatives.
在一些实施方式中，聚醚多元醇可以为例如按重量计35-45份、38-42份或40-50份，诸如30份、32份、34份、36份、40份、42份、44份、46份、48份或50份中的任一值或者任意两个点值之间的区间值；异氰酸酯可以为按重量计5-9份、6-8份或7-7.5份，诸如4份、5份、6份、7份、8份或9份中的任一值或者任意两个点值之间的区间值；催化剂可以为按重量计0.07-0.18份、0.08-0.15份或0.09-0.12份，诸如0.05份、0.07份、0.09份、0.1份、0.12份、0.14份、0.16份、0.18份或0.2份的任一值或者任意两个点值之间的区间值；扩链剂可以为按重量计0.5-0.18份、0.8-0.15份或0.1-0.14份，诸如0.5份、0.7份、0.9份、1.0份、1.2份、1.4份、1.6份、1.8份或2.0份中的任一值或者任意两个点值之间的区间值；溶剂可以为按重量计105-145份、110-140份或120-130份，诸如105份、110份、115份、120份、125份、130份、135份、140份、145份或150份中的任一值或者任意两个点值之间的区间值；抗氧剂可以为按重量计0.8-2.5份、1.0-2.0份或1.5-0.8份，诸如0.5份、0.7份、0.9份、1.0份、1.2份、1.4份、1.6份、1.8份、2.0份、2.2份、2.4份、2.6份、2.8份或3.0份中的任一值或者任意两个点值之间的区间值；有机硅耐热单体可以为按重量计6-11份、7-10份或8-9份，诸如5份、6份、7份、8份、9份、10份、11份或12份中的任一值或者任意两个点值之间的区间值；增塑剂可以为按重量计1份、1.5份、2.0份、2.5份或3.0份中的任一值或者任意两个点值之间的区间值；固化剂可以为按重量计0.7-1.8份、0.9-1.6份或1.2-1.5份，诸如0.5份、0.7份、0.9份、1.0份、1.2份、1.4份、1.6份、1.8份或2.0份中的任一值或者任意两个点值之间的区间值。In some embodiments, the polyether polyol can be, for example, 35-45 parts, 38-42 parts, or 40-50 parts by weight, such as 30 parts, 32 parts, 34 parts, 36 parts, 40 parts, 42 parts, Any value in 44, 46, 48 or 50 parts or an interval value between any two point values; the isocyanate can be 5-9 parts, 6-8 parts or 7-7.5 parts by weight, such as Any value in 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts or an interval value between any two point values; the catalyst can be 0.07-0.18 parts, 0.08-0.15 parts or 0.09-0.12 shares, such as any value of 0.05 shares, 0.07 shares, 0.09 shares, 0.1 shares, 0.12 shares, 0.14 shares, 0.16 shares, 0.18 shares or 0.2 shares or the interval value between any two point values; chain extension The agent may be in the range of 0.5-0.18, 0.8-0.15 or 0.1-0.14 parts by weight, such as 0.5, 0.7, 0.9, 1.0, 1.2, 1.4, 1.6, 1.8 or 2.0 parts Any value or an interval value between any two point values; the solvent can be 105-145 parts, 110-140 parts or 120-130 parts by weight, such as 105 parts, 110 parts, 115 parts, 120 parts, 125 parts Part, 130 parts, 135 parts, 140 parts, 145 parts or any value in 150 parts or the interval value between any two point values; Antioxidant can be by weight 0.8-2.5 parts, 1.0-2.0 parts or 1.5-0.8 parts, such as 0.5 parts, 0.7 parts, 0.9 parts, 1.0 parts, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts or 3.0 parts Any value or an interval value between any two point values; the silicone heat-resistant monomer can be 6-11 parts, 7-10 parts or 8-9 parts by weight, such as 5 parts, 6 parts, 7 parts , 8 parts, 9 parts, 10 parts, 11 parts or any value in 12 parts or an interval value between any two point values; the plasticizer can be 1 part, 1.5 parts, 2.0 parts, 2.5 parts by weight Any value in part or 3.0 part or interval value between any two point values; Curing agent can be by weight 0.7-1.8 part, 0.9-1.6 part or 1.2-1.5 part, such as 0.5 part, 0.7 part, Any value in 0.9 parts, 1.0 parts, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts or 2.0 parts or an interval value between any two point values.
在一些实施方式中，增塑剂为脱水蓖麻油、氢化蓖麻油、蓖麻油脂肪酸和蓖麻油脂肪酸酯中的一种或多种组合。In some embodiments, the plasticizer is one or more combinations of dehydrated castor oil, hydrogenated castor oil, castor oil fatty acid and castor oil fatty acid ester.
在一些实施方式中，聚醚多元醇为聚四氢呋喃醚二醇、聚丙二醇、聚氧化丙烯三醇、甘油聚醚、乙二胺聚醚四醇中的一种或多种组合。在一些实施方式中，异氰酸酯为甲苯二异氰酸酯、二苯基甲烷-4,4'-二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、异佛尔酮二异氰酸酯和甲基环已烷二异氰酸酯中 的一种或多种组合。In some embodiments, the polyether polyol is one or more combinations of polytetrahydrofuran ether diol, polypropylene glycol, polyoxypropylene triol, glycerol polyether, and ethylenediamine polyether tetraol. In some embodiments, the isocyanate is toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate , one or more combinations of lysine diisocyanate, isophorone diisocyanate and methylcyclohexane diisocyanate.
在一些实施方式中，催化剂为锡系催化剂，选自二辛基氧化锡、二丁基二氯化锡、二丁基二溴化锡、二丁基二月桂酸锡、二丁基二乙酸锡、二丁基硫化锡、三丁基三氯乙酸锡、三丁基硫化锡和二丁基二马来酸锡中的一种或多种组合。In some embodiments, the catalyst is a tin-based catalyst selected from dioctyltin oxide, dibutyltin dichloride, dibutyltin dibromide, dibutyltin dilaurate, dibutyltin diacetate , one or more combinations of dibutyltin sulfide, tributyltin trichloroacetate, tributyltin sulfide and dibutyltin dimaleate.
在一些实施方式中，扩链剂为二元胺扩链剂，选自乙二胺、1,2-丙二胺、1,6-六亚甲基二胺、异氟尔酮二胺、1,4-环己烷二胺、N-羟甲基氨基乙胺和N-乙基氨基乙胺中的一种或多种组合。In some embodiments, the chain extender is a diamine chain extender selected from ethylenediamine, 1,2-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, 1 , One or more combinations of 4-cyclohexanediamine, N-hydroxymethylaminoethylamine and N-ethylaminoethylamine.
在一些实施方式中，抗氧剂为抗氧剂1076。在一些实施方式中，溶剂为甲苯、乙酸丁酯、丙酮、环己酮、丙二醇单***和乙二醇单正丙醚中的一种或多种组合。In some embodiments, the antioxidant is Antioxidant 1076. In some embodiments, the solvent is one or more combinations of toluene, butyl acetate, acetone, cyclohexanone, propylene glycol monoethyl ether, and ethylene glycol mono-n-propyl ether.
在一些实施方式中，有机硅耐热单体为聚二甲基硅氧烷、环甲基硅氧烷、氨基硅氧烷、聚甲基苯基硅氧烷和聚醚聚硅氧烷共聚物中的一种或多种组合。In some embodiments, the silicone heat-resistant monomer is polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane, and polyether polysiloxane copolymer One or more combinations of them.
在一些实施方式中，固化剂为甲苯二异氰酸酯-三羟甲基丙烷加成物、氯苯二异氰酸-三羟甲基丙烷加成物、六亚甲基二异氰酸-三羟甲基丙烷加成物、异氟尔酮二异氰酸-三羟甲基丙烷加成物、异氰脲酸酯和缩二脲中的一种或多种。In some embodiments, the curing agent is toluene diisocyanate-trimethylolpropane adduct, chlorobenzene diisocyanate-trimethylolpropane adduct, hexamethylene diisocyanate-trimethylolpropane one or more of phenylpropane adduct, isophorone diisocyanate-trimethylolpropane adduct, isocyanurate and biuret.
本公开的一些实施方式还提供一种高性能聚氨酯压敏胶的制备方法，包括如下步骤：Some embodiments of the present disclosure also provide a method for preparing a high-performance polyurethane pressure-sensitive adhesive, comprising the steps of:
在反应釜中依次加入聚醚多元醇、异氰酸酯和溶剂重量份数的70-80％(诸如71-79％、72-78％或74-76％)，搅拌均匀后在N 2保护下，加热至35-55℃(诸如38-52℃、40-48℃或42-46℃)，然后向反应液中缓慢滴加催化剂，边搅拌边加热至70-90℃(诸如72-88℃、75-85℃或78-82℃)，滴加完毕后70-90℃(诸如72-88℃、75-85℃或78-82℃)保温反应3-6h(诸如3h、4h、5h或6h)，得到混合液A； 70-80% (such as 71-79%, 72-78% or 74-76%) of polyether polyol, isocyanate and solvent parts by weight are sequentially added in the reaction kettle, after stirring evenly, under N 2 protection, heating to 35-55°C (such as 38-52°C, 40-48°C or 42-46°C), then slowly add the catalyst dropwise to the reaction solution, and heat to 70-90°C while stirring (such as 72-88°C, 75°C -85°C or 78-82°C), after the dropwise addition is completed, keep the reaction at 70-90°C (such as 72-88°C, 75-85°C or 78-82°C) for 3-6h (such as 3h, 4h, 5h or 6h) , to obtain the mixture A;
将混合液A的温度降至40-60℃(诸如42-58℃、45-55℃或48-52℃)，然后依次加入扩链剂、增塑剂和溶剂重量份数的20-30％(诸如22-28％、23-27％或24-36％)，在40-60℃(诸如42-58℃、45-55℃或48-52℃)下保温反应1-3h(诸如1h、2h或3h)，得到混合液B；Reduce the temperature of the mixed liquid A to 40-60°C (such as 42-58°C, 45-55°C or 48-52°C), and then sequentially add chain extender, plasticizer and solvent in 20-30% by weight (such as 22-28%, 23-27% or 24-36%), at 40-60°C (such as 42-58°C, 45-55°C or 48-52°C) for 1-3h (such as 1h, 2h or 3h), to obtain the mixed solution B;
在40-60℃(诸如42-58℃、45-55℃或48-52℃)不断搅拌条件下，依次将耐热单体、抗氧剂和固化剂滴加到混合液B中，滴加完毕后搅拌10-30min(诸如14-26min、15-25min或18-22min)，然后将反应液冷却至20-30℃(诸如21-29℃、22-28℃或24-26℃)，得到聚氨酯压敏胶。Under the condition of constant stirring at 40-60°C (such as 42-58°C, 45-55°C or 48-52°C), add the heat-resistant monomer, antioxidant and curing agent dropwise to the mixed liquid B in sequence, dropwise After completion, stir for 10-30min (such as 14-26min, 15-25min or 18-22min), and then cool the reaction solution to 20-30°C (such as 21-29°C, 22-28°C or 24-26°C), to obtain Polyurethane pressure sensitive adhesive.
本公开一些实施方式还提供了一种高性能聚氨酯压敏胶在PET保护膜中的应用，方法为：将聚氨酯压敏胶均匀涂覆在50-60μm(诸如51-59μm、52-58μm或54-56μm)厚的PET基膜电晕面上，并将PET基膜置于80-100℃烘箱中烘5-10min(诸如5min、6min、7min、8min、9min或10min)至胶面干燥，控制干胶厚度为10±1μm，然后在胶面上覆50μm厚度的离型膜， 并将其置于40-50℃(诸如41-49℃、42-48℃或45-47℃)烘箱中熟化5d备用。Some embodiments of the present disclosure also provide an application of a high-performance polyurethane pressure-sensitive adhesive in a PET protective film, the method is: uniformly coating the polyurethane pressure-sensitive adhesive -56μm) thick PET base film on the corona surface, and put the PET base film in an oven at 80-100°C for 5-10min (such as 5min, 6min, 7min, 8min, 9min or 10min) until the glue surface is dry, control The thickness of the dry glue is 10±1μm, and then cover the glue surface with a release film with a thickness of 50μm, and place it in an oven at 40-50°C (such as 41-49°C, 42-48°C or 45-47°C) for curing 5d spare.
本公开一些实施方式还提供根据上文所述的一种高性能聚氨酯压敏胶在电器(诸如电线电缆接头和末端、电机线圈的绝缘保护；诸如电冰箱、洗衣机等电器导管或夹板的固定和密封)、汽车、液晶面板、通讯产品(诸如电路板在进行波峰焊时，需将不上锡的部位进行掩蔽，在喷涂时所用掩蔽胶带)、计算机和消费电子产品(诸如在超小型化的电子设备中，无引线元件包装用的压敏胶带和能热融压敏胶)中的用途。本公开提出了一种润湿效果好，剥离容易且无残胶污染，能适应高温高湿环境的一种高性能聚氨酯压敏胶及其制备方法。Some embodiments of the present disclosure also provide a high-performance polyurethane pressure-sensitive adhesive as described above in electrical appliances (such as wire and cable joints and terminals, insulation protection of motor coils; such as refrigerators, washing machines and other electrical conduits or splints. Sealing), automobiles, liquid crystal panels, communication products (such as when circuit boards are wave soldered, the parts that are not tinned need to be masked, and masking tape is used when spraying), computers and consumer electronics (such as in ultra-miniature In electronic equipment, the use of pressure-sensitive adhesive tapes and hot-melt pressure-sensitive adhesives for leadless component packaging). The disclosure proposes a high-performance polyurethane pressure-sensitive adhesive that has good wetting effect, is easy to peel off, has no residual glue pollution, and can adapt to high-temperature and high-humidity environments, and a preparation method thereof.
(1)本公开在聚氨酯压敏胶制备过程中引入了特殊的增塑剂，在有机硅耐热单体、耐热抗氧剂和增塑剂协同作用下，使得聚氨酯压敏胶具备优异的润湿性能(低于10s)、耐污染性性能，同时制备的压敏胶具有剥离力稳定、优异的耐热性能(180℃2h玻璃板无污染)，能够稳定广泛地适用于手机、汽车、面板制造等高端领域。(1) This disclosure introduces a special plasticizer in the preparation process of polyurethane pressure-sensitive adhesive. Under the synergy of silicone heat-resistant monomer, heat-resistant antioxidant and plasticizer, the polyurethane pressure-sensitive adhesive has excellent Wetting performance (less than 10s), pollution resistance performance, and the pressure-sensitive adhesive prepared at the same time has stable peeling force and excellent heat resistance (180 ° C 2h glass plate without pollution), can be widely used in mobile phones, automobiles, High-end fields such as panel manufacturing.
(2)在聚氨酯压敏胶制备过程中引入合适的扩链剂，可以有效提高聚氨酯胶水的相对分子质量，提高压敏胶的内聚力和初粘力，有效防止残胶的出现，提高了压敏胶的耐污染能力。(2) Introducing a suitable chain extender during the preparation of polyurethane pressure-sensitive adhesives can effectively increase the relative molecular weight of polyurethane glue, improve the cohesion and initial adhesion of pressure-sensitive adhesives, effectively prevent the appearance of residual glue, and improve the pressure-sensitive adhesive properties. The pollution resistance of the glue.
实施例Example
实施例1 高性能聚氨酯压敏胶的制备以及在PET保护膜中的应用Example 1 Preparation of high-performance polyurethane pressure-sensitive adhesive and its application in PET protective film
一种高性能聚氨酯压敏胶，按照重量份数计算，包括：聚醚多元醇：聚四氢呋喃醚二醇10份、聚丙二醇20份；异氰酸酯：甲苯二异氰酸酯1份、二苯基甲烷-4,4'-二异氰酸酯3份；催化剂：二辛基氧化锡0.02份、二丁基二氯化锡0.03份；扩链剂：乙二胺0.2份、1,2-丙二胺0.2份；溶剂：甲苯40份、乙酸丁酯60份；抗氧剂：抗氧剂1076 0.5份；有机硅耐热单体：聚二甲基硅氧烷2份、环甲基硅氧烷3份；增塑剂：脱水蓖麻油0.5份、氢化蓖麻油0.5份；固化剂：甲苯二异氰酸酯-三羟甲基丙烷加成物0.2份、氯苯二异氰酸-三羟甲基丙烷加成物0.3份。A high-performance polyurethane pressure-sensitive adhesive, calculated in parts by weight, comprising: polyether polyol: 10 parts of polytetrahydrofuran ether glycol, 20 parts of polypropylene glycol; isocyanate: 1 part of toluene diisocyanate, diphenylmethane-4, 3 parts of 4'-diisocyanate; catalyst: 0.02 part of dioctyltin oxide, 0.03 part of dibutyltin dichloride; chain extender: 0.2 part of ethylenediamine, 0.2 part of 1,2-propylenediamine; solvent: 40 parts of toluene, 60 parts of butyl acetate; antioxidant: 1076 0.5 parts of antioxidant; silicone heat-resistant monomer: 2 parts of polydimethylsiloxane, 3 parts of cyclomethicone; plasticizer : 0.5 part of dehydrated castor oil, 0.5 part of hydrogenated castor oil; curing agent: 0.2 part of toluene diisocyanate-trimethylolpropane adduct, 0.3 part of chlorobenzene diisocyanate-trimethylolpropane adduct.
一种高性能聚氨酯压敏胶的制备方法，包括如下步骤：A preparation method of high-performance polyurethane pressure-sensitive adhesive, comprising the steps of:
S1，在反应釜中依次加入聚醚多元醇、异氰酸酯和溶剂重量份数的70％，搅拌均匀后在N 2保护下，加热至35℃，然后向反应液中缓慢滴加催化剂，边搅拌边加热至70℃，滴加完毕后70℃保温反应3h，得到混合液A； S1, add polyether polyol, isocyanate and 70% of the weight of the solvent in sequence in the reaction kettle, stir evenly, under the protection of N2 , heat to 35 ° C, then slowly add the catalyst dropwise to the reaction solution, while stirring Heat to 70°C, and after the dropwise addition, keep the reaction at 70°C for 3 hours to obtain the mixed solution A;
S2，将混合液A的温度降至40℃，然后依次加入扩链剂、增塑剂和溶剂重量份数的30％，在40℃下保温反应1h，得到混合液B；S2, lowering the temperature of the mixed solution A to 40°C, then sequentially adding chain extender, plasticizer and 30% of the weight of the solvent, and keeping the temperature at 40°C for 1 hour to obtain the mixed solution B;
S3，在40℃不断搅拌条件下，依次将耐热单体、抗氧剂和固化剂滴加到混合液B中，滴加完毕后搅拌10min，然后将反应液冷却至20℃，得到聚氨酯压敏胶。S3, under the condition of constant stirring at 40°C, add the heat-resistant monomer, antioxidant and curing agent dropwise to the mixed solution B in sequence, stir for 10 minutes after the dropwise addition, and then cool the reaction solution to 20°C to obtain a polyurethane press Sensitive glue.
一种高性能聚氨酯压敏胶在PET保护膜中的应用，将聚氨酯压敏胶均匀涂覆在50μm厚的PET基膜电晕面上，并将PET基膜置于80℃烘箱中烘5min至胶面干燥，控制干胶厚度为9μm，然后在胶面上覆50μm厚度的离型膜，并将其置于40℃烘箱中熟化5d备用。Application of a high-performance polyurethane pressure-sensitive adhesive in PET protective film. The polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of the PET base film with a thickness of 50 μm, and the PET base film is baked in an oven at 80 ° C for 5 minutes to The glue surface was dried, and the thickness of the dry glue was controlled to be 9 μm, and then a release film with a thickness of 50 μm was covered on the glue surface, and it was placed in an oven at 40° C. for 5 d for later use.
实施例2 高性能聚氨酯压敏胶的制备以及在PET保护膜中的应用Example 2 Preparation of high-performance polyurethane pressure-sensitive adhesive and its application in PET protective film
一种高性能聚氨酯压敏胶，按照重量份数计算，包括：聚氧化丙烯三醇30份、甘油聚醚20份；异氰酸酯：苯二亚甲基二异氰酸酯2份、四甲基苯二亚甲基二异氰酸酯3份、六亚甲基二异氰酸酯5份；催化剂：二丁基二溴化锡0.5份、二丁基二月桂酸锡0.6份、二丁基二乙酸锡0.9份；扩链剂：1,6-六亚甲基二胺1份、异氟尔酮二胺1份；溶剂：丙酮70份、环己酮80份；抗氧剂：抗氧剂1076 3份；有机硅耐热单体：氨基硅氧烷5份、聚甲基苯基硅氧烷7份；增塑剂：蓖麻油脂肪酸1份、蓖麻油脂肪酸酯2份；固化剂：六亚甲基二异氰酸-三羟甲基丙烷加成物1份、异氟尔酮二异氰酸-三羟甲基丙烷加成物1份。A high-performance polyurethane pressure-sensitive adhesive, calculated in parts by weight, comprising: 30 parts of polyoxypropylene triol, 20 parts of glycerol polyether; isocyanate: 2 parts of xylylene diisocyanate, tetramethylphthalylene 3 parts of hexamethylene diisocyanate, 5 parts of hexamethylene diisocyanate; catalyst: 0.5 part of dibutyltin dibromide, 0.6 part of dibutyltin dilaurate, 0.9 part of dibutyltin diacetate; chain extender: 1 part of 1,6-hexamethylenediamine, 1 part of isophorone diamine; solvent: 70 parts of acetone, 80 parts of cyclohexanone; antioxidant: 3 parts of antioxidant 1076; silicone heat-resistant sheet Body: 5 parts of aminosiloxane, 7 parts of polymethylphenylsiloxane; plasticizer: 1 part of castor oil fatty acid, 2 parts of castor oil fatty acid ester; curing agent: hexamethylene diisocyanate- 1 part of trimethylolpropane adduct, 1 part of isophorone diisocyanate-trimethylolpropane adduct.
一种高性能聚氨酯压敏胶的制备方法，包括如下步骤：A preparation method of high-performance polyurethane pressure-sensitive adhesive, comprising the steps of:
S1，在反应釜中依次加入聚醚多元醇、异氰酸酯和溶剂重量份数的80％，搅拌均匀后在N 2保护下，加热至55℃，然后向反应液中缓慢滴加催化剂，边搅拌边加热至90℃，滴加完毕后90℃保温反应6h，得到混合液A； S1, add polyether polyol, isocyanate and 80% of the weight of the solvent in sequence in the reaction kettle, stir evenly, under the protection of N2 , heat to 55 ° C, then slowly add the catalyst dropwise to the reaction solution, while stirring Heat to 90°C, and after the dropwise addition, keep warm at 90°C for 6 hours to obtain the mixed solution A;
S2，将混合液A的温度降至60℃，然后依次加入扩链剂、增塑剂和溶剂重量份数的20％，在60℃下保温反应3h，得到混合液B；S2, the temperature of the mixed solution A is lowered to 60° C., and then sequentially add chain extender, plasticizer and 20% by weight of the solvent, and keep warm at 60° C. for 3 hours to obtain the mixed solution B;
S3，在60℃不断搅拌条件下，依次将耐热单体、抗氧剂和固化剂滴加到混合液B中，滴加完毕后搅拌30min，然后将反应液冷却至30℃，得到聚氨酯压敏胶。S3, under the condition of constant stirring at 60°C, add the heat-resistant monomer, antioxidant and curing agent dropwise to the mixed solution B in sequence, stir for 30 minutes after the dropwise addition, and then cool the reaction solution to 30°C to obtain a polyurethane press Sensitive glue.
一种高性能聚氨酯压敏胶在PET保护膜中的应用，将聚氨酯压敏胶均匀涂覆在60μm厚的PET基膜电晕面上，并将PET基膜置于100℃烘箱中烘10min至胶面干燥，控制干胶厚度为11μm，然后在胶面上覆50μm厚度的离型膜，并将其置于50℃烘箱中熟化5d备用。Application of a high-performance polyurethane pressure-sensitive adhesive in a PET protective film. The polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of a 60 μm thick PET base film, and the PET base film is baked in an oven at 100°C for 10 minutes to The glue surface is dried, and the thickness of the dry glue is controlled to be 11 μm, and then a release film with a thickness of 50 μm is covered on the glue surface, and it is placed in an oven at 50° C. for 5 d for later use.
实施例3 高性能聚氨酯压敏胶的制备以及在PET保护膜中的应用Example 3 Preparation of high-performance polyurethane pressure-sensitive adhesive and its application in PET protective film
一种高性能聚氨酯压敏胶，按照重量份数计算，包括：聚醚多元醇：甘油聚醚10份、乙二胺聚醚四醇25份；异氰酸酯：赖氨酸二异氰酸酯1份、异佛尔酮二异氰酸酯2份、甲基环已烷二异氰酸酯2份；催化剂：二丁基硫化锡0.3、三丁基三氯乙酸锡0.3份、三丁基硫化锡0.3份；扩链剂：1,4-环己烷二胺0.2份、N-羟甲基氨基乙胺0.3份、N-乙基氨基乙胺0.2份；溶剂：丙二醇单***60份、乙二醇单正丙醚50份；抗氧剂：抗氧剂1076 1份；有机硅耐热单体：聚甲基苯基硅氧烷3份、聚醚聚硅氧烷共聚物4份；增塑剂：脱水蓖麻油1份、蓖麻 油脂肪酸酯1份；固化剂：异氰脲酸酯0.5份、缩二脲0.3份；A high-performance polyurethane pressure-sensitive adhesive, calculated in parts by weight, comprising: polyether polyol: 10 parts of glycerol polyether, 25 parts of ethylenediamine polyether tetraol; isocyanate: 1 part of lysine diisocyanate, isofor 2 parts of ketone diisocyanate, 2 parts of methyl cyclohexane diisocyanate; Catalyst: 0.3 parts of dibutyl tin sulfide, 0.3 parts of tributyl tin trichloroacetate, 0.3 parts of tributyl tin sulfide; Chain extender: 1, 0.2 parts of 4-cyclohexanediamine, 0.3 parts of N-hydroxymethylaminoethylamine, 0.2 parts of N-ethylaminoethylamine; solvent: 60 parts of propylene glycol monoethyl ether, 50 parts of ethylene glycol mono-n-propyl ether; Oxygen agent: 1 part of antioxidant 1076; silicone heat-resistant monomer: 3 parts of polymethylphenylsiloxane, 4 parts of polyether polysiloxane copolymer; plasticizer: 1 part of dehydrated castor oil, castor 1 part of sesame oil fatty acid ester; curing agent: 0.5 part of isocyanurate, 0.3 part of biuret;
一种高性能聚氨酯压敏胶的制备方法，包括如下步骤：A preparation method of high-performance polyurethane pressure-sensitive adhesive, comprising the steps of:
S1，在反应釜中依次加入聚醚多元醇、异氰酸酯和溶剂重量份数的72％，搅拌均匀后在N 2保护下，加热至38℃，然后向反应液中缓慢滴加催化剂，边搅拌边加热至75℃，滴加完毕后75℃保温反应4h，得到混合液A； S1, add polyether polyol, isocyanate and 72% of the weight of the solvent in sequence in the reaction kettle, stir evenly, under the protection of N2 , heat to 38 ° C, then slowly add the catalyst dropwise to the reaction solution, while stirring Heat to 75°C, and after the dropwise addition, keep the reaction at 75°C for 4 hours to obtain the mixed solution A;
S2，将混合液A的温度降至45℃，然后依次加入扩链剂、增塑剂和溶剂重量份数的28％，在45℃下保温反应1.5h，得到混合液B；S2, the temperature of the mixed solution A is lowered to 45°C, and then sequentially add chain extender, plasticizer and 28% of the weight of the solvent, and keep warm at 45°C for 1.5h to obtain the mixed solution B;
S3，在45℃不断搅拌条件下，依次将耐热单体、抗氧剂和固化剂滴加到混合液B中，滴加完毕后搅拌15min，然后将反应液冷却至25℃，得到聚氨酯压敏胶。S3, under the condition of constant stirring at 45°C, add the heat-resistant monomer, antioxidant and curing agent dropwise to the mixed liquid B in sequence, stir for 15 minutes after the dropwise addition, and then cool the reaction liquid to 25°C to obtain a polyurethane press Sensitive glue.
一种高性能聚氨酯压敏胶在PET保护膜中的应用，将聚氨酯压敏胶均匀涂覆在55μm厚的PET基膜电晕面上，并将PET基膜置于85℃烘箱中烘6min至胶面干燥，控制干胶厚度为10μm，然后在胶面上覆50μm厚度的离型膜，并将其置于45℃烘箱中熟化5d备用。Application of a high-performance polyurethane pressure-sensitive adhesive in PET protective film. The polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of the PET base film with a thickness of 55 μm, and the PET base film is baked in an oven at 85 ° C for 6 minutes to The glue surface is dried, and the thickness of the dry glue is controlled to be 10 μm, and then a release film with a thickness of 50 μm is covered on the glue surface, and it is placed in an oven at 45° C. for 5 d for later use.
实施例4 高性能聚氨酯压敏胶的制备以及在PET保护膜中的应用Example 4 Preparation of high-performance polyurethane pressure-sensitive adhesive and its application in PET protective film
一种高性能聚氨酯压敏胶，按照重量份数计算，包括：聚醚多元醇：聚四氢呋喃醚二醇15份、甘油聚醚15份、乙二胺聚醚四醇15份；异氰酸酯：二苯基甲烷-4,4'-二异氰酸酯2份、四甲基苯二亚甲基二异氰酸酯2份、赖氨酸二异氰酸酯2份；催化剂：二辛基氧化锡0.04份、三丁基三氯乙酸锡0.04份、二丁基二马来酸锡0.04份；扩链剂：1,6-六亚甲基二胺0.3份、异氟尔酮二胺0.3份、N-乙基氨基乙胺0.4份；溶剂：甲苯50份、丙酮70份；抗氧剂：抗氧剂1076 1.5份；有机硅耐热单体：聚二甲基硅氧烷2份、氨基硅氧烷3份、聚甲基苯基硅氧烷3份；增塑剂：脱水蓖麻油0.7份、蓖麻油脂肪酸酯0.8份；固化剂：甲苯二异氰酸酯-三羟甲基丙烷加成物0.5份、异氟尔酮二异氰酸-三羟甲基丙烷加成物0.5份。A high-performance polyurethane pressure-sensitive adhesive, calculated in parts by weight, comprising: polyether polyol: 15 parts of polytetrahydrofuran ether glycol, 15 parts of glycerol polyether, 15 parts of ethylenediamine polyether tetraol; isocyanate: diphenyl 2 parts of methyl methane-4,4'-diisocyanate, 2 parts of tetramethylxylylene diisocyanate, 2 parts of lysine diisocyanate; Catalyst: 0.04 parts of dioctyltin oxide, tributyl trichloroacetic acid 0.04 parts of tin, 0.04 parts of dibutyltin dimaleate; chain extender: 0.3 parts of 1,6-hexamethylenediamine, 0.3 parts of isophorone diamine, 0.4 parts of N-ethylaminoethylamine ; Solvent: 50 parts of toluene, 70 parts of acetone; Antioxidant: 1.5 parts of antioxidant 1076; Silicone heat-resistant monomer: 2 parts of polydimethylsiloxane, 3 parts of aminosiloxane, polymethylbenzene 3 parts of polysiloxane; plasticizer: 0.7 part of dehydrated castor oil, 0.8 part of castor oil fatty acid ester; curing agent: 0.5 part of toluene diisocyanate-trimethylolpropane adduct, isophorone diisocyanate Acid-trimethylolpropane adduct 0.5 part.
一种高性能聚氨酯压敏胶的制备方法，包括如下步骤：A preparation method of high-performance polyurethane pressure-sensitive adhesive, comprising the steps of:
S1，在反应釜中依次加入聚醚多元醇、异氰酸酯和溶剂重量份数的75％，搅拌均匀后在N 2保护下，加热至45℃，然后向反应液中缓慢滴加催化剂，边搅拌边加热至80℃，滴加完毕后80℃保温反应4h，得到混合液A； S1, add polyether polyol, isocyanate and 75% of the weight of the solvent in sequence in the reaction kettle, stir evenly, under the protection of N2 , heat to 45 ° C, then slowly add the catalyst dropwise to the reaction solution, while stirring Heat to 80°C, and after the dropwise addition, keep the temperature at 80°C for 4 hours to obtain the mixed solution A;
S2，将混合液A的温度降至45℃，然后依次加入扩链剂、增塑剂和溶剂重量份数的25％，在45℃下保温反应1.5h，得到混合液B；S2, the temperature of the mixed solution A is lowered to 45°C, and then sequentially add chain extender, plasticizer and 25% of the weight of the solvent, and keep warm at 45°C for 1.5h to obtain the mixed solution B;
S3，在45℃不断搅拌条件下，依次将耐热单体、抗氧剂和固化剂滴加到混合液B中，滴加完毕后搅拌25min，然后将反应液冷却至25℃，得到聚氨酯压敏胶。S3, under the condition of constant stirring at 45°C, add the heat-resistant monomer, antioxidant and curing agent dropwise to the mixed liquid B in sequence, stir for 25 minutes after the dropwise addition, and then cool the reaction liquid to 25°C to obtain a polyurethane press Sensitive glue.
一种高性能聚氨酯压敏胶在PET保护膜中的应用，将聚氨酯压敏胶均匀涂覆在50μm厚 的PET基膜电晕面上，并将PET基膜置于95℃烘箱中烘8min至胶面干燥，控制干胶厚度为10μm，然后在胶面上覆50μm厚度的离型膜，并将其置于45℃烘箱中熟化5d备用。Application of a high-performance polyurethane pressure-sensitive adhesive in PET protective film. The polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of the PET base film with a thickness of 50 μm, and the PET base film is baked in an oven at 95 ° C for 8 minutes to The glue surface is dried, and the thickness of the dry glue is controlled to be 10 μm, and then a release film with a thickness of 50 μm is covered on the glue surface, and it is placed in an oven at 45° C. for 5 d for later use.
实施例5 高性能聚氨酯压敏胶的制备以及在PET保护膜中的应用Example 5 Preparation of high-performance polyurethane pressure-sensitive adhesive and its application in PET protective film
一种高性能聚氨酯压敏胶，按照重量份数计算，包括：聚醚多元醇：聚四氢呋喃醚二醇10份、聚丙二醇10份、乙二胺聚醚四醇20份；异氰酸酯：二苯基甲烷-4,4'-二异氰酸酯2份、异佛尔酮二异氰酸酯2份、甲基环已烷二异氰酸酯3份；催化剂：二丁基二溴化锡0.05份、二丁基硫化锡0.05份、三丁基三氯乙酸锡0.05份；扩链剂：异氟尔酮二胺0.5份、1,4-环己烷二胺0.5份、N-乙基氨基乙胺0.5份；溶剂：乙酸丁酯60份、环己酮70份；抗氧剂：抗氧剂1076 2份；有机硅耐热单体：环甲基硅氧烷3份、聚甲基苯基硅氧烷3份、聚醚聚硅氧烷共聚物3份；增塑剂：氢化蓖麻油1份、蓖麻油脂肪酸酯1.5份；固化剂：甲苯二异氰酸酯-三羟甲基丙烷加成物0.5份、异氟尔酮二异氰酸-三羟甲基丙烷加成物0.5份、缩二脲0.5份。A high-performance polyurethane pressure-sensitive adhesive, calculated in parts by weight, comprising: polyether polyol: 10 parts of polytetrahydrofuran ether glycol, 10 parts of polypropylene glycol, 20 parts of ethylenediamine polyether tetraol; isocyanate: diphenyl 2 parts of methane-4,4'-diisocyanate, 2 parts of isophorone diisocyanate, 3 parts of methylcyclohexane diisocyanate; catalyst: 0.05 parts of dibutyl tin dibromide, 0.05 parts of dibutyl tin sulfide , 0.05 part of tributyltin trichloroacetate; chain extender: 0.5 part of isophorone diamine, 0.5 part of 1,4-cyclohexanediamine, 0.5 part of N-ethylaminoethylamine; solvent: butyl acetate 60 parts of ester, 70 parts of cyclohexanone; antioxidant: 2 parts of antioxidant 1076; silicone heat-resistant monomer: 3 parts of cyclomethicone, 3 parts of polymethylphenylsiloxane, polyether 3 parts of polysiloxane copolymer; plasticizer: 1 part of hydrogenated castor oil, 1.5 parts of castor oil fatty acid ester; curing agent: 0.5 part of toluene diisocyanate-trimethylol propane adduct, 0.5 part of isophorone di 0.5 part of isocyanic acid-trimethylolpropane adduct, 0.5 part of biuret.
一种高性能聚氨酯压敏胶的制备方法，包括如下步骤：A preparation method of high-performance polyurethane pressure-sensitive adhesive, comprising the steps of:
S1，在反应釜中依次加入聚醚多元醇、异氰酸酯和溶剂重量份数的74％，搅拌均匀后在N 2保护下，加热至40℃，然后向反应液中缓慢滴加催化剂，边搅拌边加热至80℃，滴加完毕后80℃保温反应5h，得到混合液A； S1, add polyether polyol, isocyanate and 74% of the weight of the solvent in sequence in the reaction kettle, stir evenly, under the protection of N2 , heat to 40 ° C, then slowly add the catalyst dropwise to the reaction solution, while stirring Heat to 80°C, and after the dropwise addition, keep the reaction at 80°C for 5 hours to obtain the mixed solution A;
S2，将混合液A的温度降至55℃，然后依次加入扩链剂、增塑剂和溶剂重量份数的26％，在55℃下保温反应2.5h，得到混合液B；S2, lowering the temperature of the mixed solution A to 55°C, then sequentially adding chain extenders, plasticizers and 26% by weight of the solvent, and keeping the temperature at 55°C for 2.5 hours to obtain the mixed solution B;
S3，在60℃不断搅拌条件下，依次将耐热单体、抗氧剂和固化剂滴加到混合液B中，滴加完毕后搅拌20min，然后将反应液冷却至25℃，得到聚氨酯压敏胶。S3, under the condition of constant stirring at 60°C, add the heat-resistant monomer, antioxidant and curing agent dropwise to the mixed solution B in sequence, stir for 20 minutes after the dropwise addition, and then cool the reaction solution to 25°C to obtain a polyurethane press Sensitive glue.
一种高性能聚氨酯压敏胶在PET保护膜中的应用，将聚氨酯压敏胶均匀涂覆在60μm厚的PET基膜电晕面上，并将PET基膜置于100℃烘箱中烘5min至胶面干燥，控制干胶厚度为11μm，然后在胶面上覆50μm厚度的离型膜，并将其置于50℃烘箱中熟化5d备用。Application of a high-performance polyurethane pressure-sensitive adhesive in PET protective film. The polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of the PET base film with a thickness of 60 μm, and the PET base film is baked in an oven at 100 ° C for 5 minutes to The glue surface is dried, and the thickness of the dry glue is controlled to be 11 μm, and then a release film with a thickness of 50 μm is covered on the glue surface, and it is placed in an oven at 50° C. for 5 d for later use.
实施例6 高性能聚氨酯压敏胶的制备以及在PET保护膜中的应用Example 6 Preparation of high-performance polyurethane pressure-sensitive adhesive and its application in PET protective film
一种高性能聚氨酯压敏胶，按照重量份数计算，包括：聚醚多元醇：聚四氢呋喃醚二醇10份、聚氧化丙烯三醇14份、乙二胺聚醚四醇14份；异氰酸酯：甲苯二异氰酸酯2份、苯二亚甲基二异氰酸酯2份、六亚甲基二异氰酸酯2份、赖氨酸二异氰酸酯份3份；催化剂：二辛基氧化锡0.03份、三丁基三氯乙酸锡0.04份、三丁基硫化锡0.05份、二丁基二马来酸锡0.06份；扩链剂：1,2-丙二胺0.6份、异氟尔酮二胺0.3份、1,4-环己烷二胺0.5份、N-羟甲基氨基乙胺0.4份；溶剂：乙酸丁酯60份、丙酮50份、丙二醇单***30份；抗氧剂：抗 氧剂1076 2.5份；有机硅耐热单体：氨基硅氧烷2份、聚甲基苯基硅氧烷3份、聚醚聚硅氧烷共聚物5份；增塑剂：脱水蓖麻油1份、氢化蓖麻油1.4份、蓖麻油脂肪酸0.4份；固化剂：甲苯二异氰酸酯-三羟甲基丙烷加成物0.7份、氯苯二异氰酸-三羟甲基丙烷加成物0.7份、异氟尔酮二异氰酸-三羟甲基丙烷加成物0.7份、异氰脲酸酯0.7份。A high-performance polyurethane pressure-sensitive adhesive, calculated in parts by weight, comprising: polyether polyol: 10 parts of polytetrahydrofuran ether glycol, 14 parts of polyoxypropylene triol, 14 parts of ethylenediamine polyether tetraol; isocyanate: 2 parts of toluene diisocyanate, 2 parts of xylylene diisocyanate, 2 parts of hexamethylene diisocyanate, 3 parts of lysine diisocyanate; catalyst: 0.03 parts of dioctyltin oxide, tributyl trichloroacetic acid 0.04 parts of tin, 0.05 parts of tributyltin sulfide, 0.06 parts of dibutyltin dimaleate; chain extenders: 0.6 parts of 1,2-propanediamine, 0.3 parts of isophorone diamine, 0.3 parts of 1,4- 0.5 parts of cyclohexanediamine, 0.4 parts of N-hydroxymethylaminoethylamine; solvent: 60 parts of butyl acetate, 50 parts of acetone, 30 parts of propylene glycol monoethyl ether; antioxidant: 2.5 parts of antioxidant 1076; organic silicon Heat-resistant monomer: 2 parts of aminosiloxane, 3 parts of polymethylphenylsiloxane, 5 parts of polyether polysiloxane copolymer; plasticizer: 1 part of dehydrated castor oil, 1.4 parts of hydrogenated castor oil, 0.4 part of castor oil fatty acid; curing agent: 0.7 part of toluene diisocyanate-trimethylolpropane adduct, 0.7 part of chlorobenzene diisocyanate-trimethylolpropane adduct, isophorone diisocyanate - 0.7 part of trimethylolpropane adduct, 0.7 part of isocyanurate.
一种高性能聚氨酯压敏胶的制备方法，包括如下步骤：A preparation method of high-performance polyurethane pressure-sensitive adhesive, comprising the steps of:
S1，在反应釜中依次加入聚醚多元醇、异氰酸酯和溶剂重量份数的73％，搅拌均匀后在N 2保护下，加热至50℃，然后向反应液中缓慢滴加催化剂，边搅拌边加热至85℃，滴加完毕后85℃保温反应5h，得到混合液A； S1, add polyether polyol, isocyanate and 73% of the weight of the solvent in sequence in the reaction kettle, stir evenly, under the protection of N2 , heat to 50 ° C, then slowly add the catalyst dropwise to the reaction solution, while stirring Heat to 85°C, and after the dropwise addition, keep the reaction at 85°C for 5 hours to obtain the mixed solution A;
S2，将混合液A的温度降至45℃，然后依次加入扩链剂、增塑剂和溶剂重量份数的27％，在45℃下保温反应1.5h，得到混合液B；S2, the temperature of the mixed solution A is lowered to 45°C, and then sequentially add chain extender, plasticizer and 27% of the weight of the solvent, and keep the temperature at 45°C for 1.5h to obtain the mixed solution B;
S3，在55℃不断搅拌条件下，依次将耐热单体、抗氧剂和固化剂滴加到混合液B中，滴加完毕后搅拌25min，然后将反应液冷却至25℃，得到聚氨酯压敏胶。S3, under the condition of continuous stirring at 55°C, add the heat-resistant monomer, antioxidant and curing agent dropwise to the mixed liquid B in sequence, stir for 25 minutes after the dropwise addition, and then cool the reaction liquid to 25°C to obtain a polyurethane press Sensitive glue.
一种高性能聚氨酯压敏胶在PET保护膜中的应用，将聚氨酯压敏胶均匀涂覆在50μm厚的PET基膜电晕面上，并将PET基膜置于85℃烘箱中烘5min至胶面干燥，控制干胶厚度为10μm，然后在胶面上覆50μm厚度的离型膜，并将其置于40℃烘箱中熟化5d备用。Application of a high-performance polyurethane pressure-sensitive adhesive in PET protective film. The polyurethane pressure-sensitive adhesive is evenly coated on the corona surface of the PET base film with a thickness of 50 μm, and the PET base film is baked in an oven at 85 ° C for 5 minutes to The glue surface was dried, and the thickness of the dry glue was controlled to be 10 μm, and then a release film with a thickness of 50 μm was covered on the glue surface, and it was placed in an oven at 40° C. for 5 d for later use.
对比例1Comparative example 1
以缺少增塑剂的实施例1为对比例1，其余组分与实施例1相同，制备方法和应用也相同。Taking Example 1 lacking plasticizer as Comparative Example 1, the remaining components are the same as Example 1, and the preparation method and application are also the same.
对比例2Comparative example 2
以缺少有机硅耐热单体的实施例1为对比例2，其余组分与实施例1相同，制备方法和应用也相同。Taking Example 1 lacking silicone heat-resistant monomer as Comparative Example 2, the remaining components are the same as Example 1, and the preparation method and application are also the same.
对比例3Comparative example 3
以缺少扩链剂的实施例1为对比例3，其余组分与实施例1相同，制备方法和应用也相同。Taking Example 1 lacking a chain extender as Comparative Example 3, the remaining components are the same as Example 1, and the preparation method and application are also the same.
对比例4Comparative example 4
以缺少增塑剂、有机硅耐热单体和扩链剂的实施例1为对比例4，其余组分与实施例1相同，制备方法和应用也相同。Taking Example 1 lacking plasticizer, silicone heat-resistant monomer and chain extender as Comparative Example 4, the remaining components are the same as Example 1, and the preparation method and application are also the same.
实验例Experimental example
将由以上实施例1-6以及对比例1-4制备的聚氨酯压敏胶涂覆的PET保护膜进行以下测试，以检测聚氨酯压敏胶的特性。The PET protective film coated with the polyurethane pressure-sensitive adhesive prepared in the above Examples 1-6 and Comparative Examples 1-4 was subjected to the following tests to detect the properties of the polyurethane pressure-sensitive adhesive.
测试方法如下：The test method is as follows:
聚氨酯压敏胶的性能测试：Performance test of polyurethane pressure sensitive adhesive:
剥离力测试：按照GB 2792-1998标准测试方法测试，将保护膜带胶面贴敷于SU304不锈钢板上，浸润30min，测试条件为23±2℃，湿度为65±5％，测量180°方向对不锈钢板的剥离力，单位为gf/25mm。Peeling force test: test according to GB 2792-1998 standard test method, stick the protective film with rubber surface on SU304 stainless steel plate, soak for 30min, test condition is 23±2℃, humidity is 65±5%, measure in 180° direction Peeling force to stainless steel plate, the unit is gf/25mm.
剥离力增长测试：另外测试烘箱120℃1h冷却至室温后的剥离力。Peel force growth test: In addition, test the peel force after cooling to room temperature in an oven at 120°C for 1 hour.
耐热性能测试：将裁好的宽25mm的PET保护膜分别贴附在钢板和玻璃上，放在烘箱中烘180℃2h，冷却至室温后，撕掉后看玻璃板和钢板上有无残胶。Heat resistance test: Attach the cut PET protective film with a width of 25mm on the steel plate and glass respectively, put it in an oven and bake at 180°C for 2 hours, after cooling to room temperature, tear it off and see if there is any residue on the glass plate and steel plate glue.
对玻璃的耐湿热性测试：将制备的PET保护膜贴附在干净的玻璃盖板两面，置于温度85℃和湿度85％的环境中放置15d，撕去PET保护膜时，观察玻璃表面有无污染(斑影、残胶等)。Humidity and heat resistance test for glass: Attach the prepared PET protective film on both sides of a clean glass cover, place it in an environment with a temperature of 85°C and a humidity of 85% for 15 days, and when the PET protective film is removed, observe the glass surface. No pollution (speckle shadow, residual glue, etc.).
对玻璃的润湿性测试：裁剪100mm×100mm的PET保护膜片，贴附在玻璃盖板上，记录保护膜完全润湿贴合玻璃盖板的时间，直至完全无气泡为止。评价标准：优(＜10s)；良(10-20s)；差(＞20s)。Wettability test for glass: Cut out a 100mm×100mm PET protective film, attach it to the glass cover, and record the time until the protective film is completely wetted and attached to the glass cover until there are no bubbles. Evaluation criteria: excellent (<10s); good (10-20s); poor (>20s).
表1性能测试结果统计Table 1 Statistics of performance test results
Figure PCTCN2022116014-appb-000001
Figure PCTCN2022116014-appb-000001
Figure PCTCN2022116014-appb-000002
Figure PCTCN2022116014-appb-000002
从表1实验数据可以分析得出，与对比例相比，本公开的聚氨酯压敏胶具有润湿性好、高温剥离力增长小、耐湿热、180℃2h无残胶无斑影的优点。由此表明：在聚氨酯压敏胶制备过程中引入特殊的增塑剂、有机硅耐热单体、耐热抗氧剂，可以使得聚氨酯压敏胶具备优异的润湿性能、耐污染性性能，同时制备的压敏胶具有剥离力稳定和优异的耐热性能；引入合适的扩链剂，可以有效提高聚氨酯胶水的相对分子质量，提高压敏胶的内聚力和初粘力，有效防止残胶的出现，提高了压敏胶的耐污染能力，能够稳定广泛的适用于手机、汽车、面板制造等高端领域。From the experimental data in Table 1, it can be concluded that, compared with the comparative example, the polyurethane pressure-sensitive adhesive of the present disclosure has the advantages of good wettability, small increase in high-temperature peeling force, heat and humidity resistance, and no adhesive residue or speckle at 180°C for 2 hours. This shows that the introduction of special plasticizers, silicone heat-resistant monomers, and heat-resistant antioxidants during the preparation of polyurethane pressure-sensitive adhesives can make polyurethane pressure-sensitive adhesives have excellent wettability and pollution resistance. The pressure-sensitive adhesive prepared at the same time has stable peeling force and excellent heat resistance; the introduction of a suitable chain extender can effectively improve the relative molecular weight of the polyurethane glue, improve the cohesion and initial adhesion of the pressure-sensitive adhesive, and effectively prevent residual glue. Appearance, improve the pollution resistance of pressure-sensitive adhesives, can be widely used in high-end fields such as mobile phones, automobiles, and panel manufacturing.
以上所述仅为本公开可选的实施方式而已，并不用以限制本公开，凡在本公开的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。The above descriptions are only optional implementations of the present disclosure, and are not intended to limit the present disclosure. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present disclosure shall be included in the present disclosure. within the scope of protection.
工业实用性Industrial Applicability
本公开提供了一种高性能聚氨酯压敏胶，该聚氨酯压敏胶对粘附物具有良好的润湿性，即使在高温和/或高湿条件下剥离力依然稳定无增长，耐污染性强，能够满足在高温场景的使用需求，因此具有优异的工业实用性。The disclosure provides a high-performance polyurethane pressure-sensitive adhesive. The polyurethane pressure-sensitive adhesive has good wettability to the adherend, and the peeling force is still stable without increasing even under high temperature and/or high humidity conditions, and has strong pollution resistance. , can meet the use requirements in high-temperature scenes, and therefore has excellent industrial applicability.

Claims (11)

  1. 一种高性能聚氨酯压敏胶，其特征在于：按照重量份数计算，包括：聚醚多元醇30-50份、异氰酸酯4-10份、催化剂0.05-0.2份、扩链剂0.4-2份、溶剂100-150份、抗氧剂0.5-3份、有机硅耐热单体5-12份、增塑剂1-3份和固化剂0.5-2份；所述增塑剂为蓖麻油及其衍生物中的一种或多种组合。A high-performance polyurethane pressure-sensitive adhesive, characterized in that: calculated in parts by weight, comprising: 30-50 parts of polyether polyol, 4-10 parts of isocyanate, 0.05-0.2 parts of catalyst, 0.4-2 parts of chain extender, 100-150 parts of solvent, 0.5-3 parts of antioxidant, 5-12 parts of silicone heat-resistant monomer, 1-3 parts of plasticizer and 0.5-2 parts of curing agent; the plasticizer is castor oil and its One or more combinations of derivatives.
  2. 如权利要求1所述的一种高性能聚氨酯压敏胶，其特征在于：所述增塑剂为脱水蓖麻油、氢化蓖麻油、蓖麻油脂肪酸和蓖麻油脂肪酸酯中的一种或多种组合。A kind of high-performance polyurethane pressure-sensitive adhesive as claimed in claim 1, is characterized in that: described plasticizer is one or more in dehydrated castor oil, hydrogenated castor oil, castor oil fatty acid and castor oil fatty acid ester combination.
  3. 如权利要求1或2所述的一种高性能聚氨酯压敏胶，其特征在于：所述聚醚多元醇为聚四氢呋喃醚二醇、聚丙二醇、聚氧化丙烯三醇、甘油聚醚、乙二胺聚醚四醇中的一种或多种组合；所述异氰酸酯为甲苯二异氰酸酯、二苯基甲烷-4,4'-二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、异佛尔酮二异氰酸酯和甲基环已烷二异氰酸酯中的一种或多种组合。A high-performance polyurethane pressure-sensitive adhesive as claimed in claim 1 or 2, characterized in that: the polyether polyol is polytetrahydrofuran ether glycol, polypropylene glycol, polypropylene oxide triol, glycerol polyether, ethylene glycol One or more combinations of amine polyether tetraols; the isocyanate is toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, tetramethylphthalylene One or more combinations of diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate and methylcyclohexane diisocyanate.
  4. 如权利要求1-3中任一项所述的一种高性能聚氨酯压敏胶，其特征在于：所述催化剂为锡系催化剂，选自二辛基氧化锡、二丁基二氯化锡、二丁基二溴化锡、二丁基二月桂酸锡、二丁基二乙酸锡、二丁基硫化锡、三丁基三氯乙酸锡、三丁基硫化锡和二丁基二马来酸锡中的一种或多种组合。A high-performance polyurethane pressure-sensitive adhesive as claimed in any one of claims 1-3, characterized in that: the catalyst is a tin-based catalyst selected from dioctyltin oxide, dibutyltin dichloride, Dibutyltin dibromide, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin trichloroacetate, tributyltin sulfide, and dibutyl dimaleate One or more combinations of tin.
  5. 如权利要求1-4中任一项所述的一种高性能聚氨酯压敏胶，其特征在于：所述扩链剂为二元胺扩链剂，选自乙二胺、1,2-丙二胺、1,6-六亚甲基二胺、异氟尔酮二胺、1,4-环己烷二胺、N-羟甲基氨基乙胺和N-乙基氨基乙胺中的一种或多种组合。A high-performance polyurethane pressure-sensitive adhesive as claimed in any one of claims 1-4, wherein the chain extender is a diamine chain extender selected from ethylenediamine, 1,2-propane One of diamine, 1,6-hexamethylenediamine, isophoronediamine, 1,4-cyclohexanediamine, N-hydroxymethylaminoethylamine and N-ethylaminoethylamine one or more combinations.
  6. 如权利要求1-5中任一项所述的一种高性能聚氨酯压敏胶，其特征在于：所述抗氧剂为抗氧剂1076；所述溶剂为甲苯、乙酸丁酯、丙酮、环己酮、丙二醇单***和乙二醇单正丙醚中的一种或多种组合。A high-performance polyurethane pressure-sensitive adhesive as claimed in any one of claims 1-5, characterized in that: the antioxidant is antioxidant 1076; the solvent is toluene, butyl acetate, acetone, cyclic One or more combinations of hexanone, propylene glycol monoethyl ether and ethylene glycol mono-n-propyl ether.
  7. 如权利要求1-6中任一项所述的一种高性能聚氨酯压敏胶，其特征在于：所述有机硅耐热单体为聚二甲基硅氧烷、环甲基硅氧烷、氨基硅氧烷、聚甲基苯基硅氧烷和聚醚聚硅氧烷共聚物中的一种或多种组合。A high-performance polyurethane pressure-sensitive adhesive as claimed in any one of claims 1-6, characterized in that: the silicone heat-resistant monomer is polydimethylsiloxane, cyclomethicone, One or more combination of aminosiloxane, polymethylphenylsiloxane and polyether polysiloxane copolymer.
  8. 如权利要求1-7中任一项所述的一种高性能聚氨酯压敏胶，其特征在于：所述固化剂为甲苯二异氰酸酯-三羟甲基丙烷加成物、氯苯二异氰酸-三羟甲基丙烷加成物、六亚甲基二异氰酸-三羟甲基丙烷加成物、异氟尔酮二异氰酸-三羟甲基丙烷加成物、异氰脲酸酯和缩二脲中的一种或多种。A high-performance polyurethane pressure-sensitive adhesive as claimed in any one of claims 1-7, wherein the curing agent is toluene diisocyanate-trimethylolpropane adduct, chlorophenyl diisocyanate -Trimethylolpropane adduct, hexamethylene diisocyanate-trimethylolpropane adduct, isophorone diisocyanate-trimethylolpropane adduct, isocyanuric acid One or more of esters and biurets.
  9. 一种制备根据权利要求1-8任一所述的一种高性能聚氨酯压敏胶的方法，其特征在于：包括如下步骤：A method for preparing a high-performance polyurethane pressure-sensitive adhesive according to any one of claims 1-8, characterized in that: comprising the steps of:
    S1，在反应釜中依次加入聚醚多元醇、异氰酸酯和溶剂重量份数的70-80％，搅拌均匀后在N 2保护下，将反应液加热至35-55℃，然后向反应液中缓慢滴加催化剂，边搅拌边加热至70-90℃，滴加完毕后70-90℃保温反应3-6h，得到混合液A； S1, add polyether polyol, isocyanate and 70-80% of the weight of the solvent in sequence in the reaction kettle, stir evenly, and under the protection of N2 , heat the reaction solution to 35-55°C, and then slowly add to the reaction solution Add the catalyst dropwise, and heat to 70-90°C while stirring. After the dropwise addition, keep the reaction at 70-90°C for 3-6h to obtain the mixed solution A;
    S2，将混合液A的温度降至40-60℃，然后依次加入扩链剂、增塑剂和溶剂重量份数的20-30％，在40-60℃下保温反应1-3h，得到混合液B；S2, lower the temperature of the mixed liquid A to 40-60°C, then sequentially add chain extender, plasticizer and 20-30% by weight of the solvent, and keep warm at 40-60°C for 1-3h to obtain a mixed Liquid B;
    S3，在40-60℃不断搅拌条件下，依次将耐热单体、抗氧剂和固化剂滴加到混合液B中，滴加完毕后搅拌10-30min，然后将反应液冷却至20-30℃，得到聚氨酯压敏胶。S3, under the condition of constant stirring at 40-60°C, add the heat-resistant monomer, antioxidant and curing agent dropwise to the mixed solution B in sequence, stir for 10-30min after the dropwise addition, and then cool the reaction solution to 20- 30°C to obtain a polyurethane pressure-sensitive adhesive.
  10. 一种根据权利要求1-8任一所述的一种高性能聚氨酯压敏胶在PET保护膜中的应用，其特征在于：将聚氨酯压敏胶均匀涂覆在50-60μm厚的PET基膜电晕面上，并将PET基膜置于80-100℃烘箱中烘5-10min至胶面干燥，控制干胶厚度为10±1μm，然后在胶面上覆50μm厚度的离型膜，并将其置于40-50℃烘箱中熟化5d备用。An application of a high-performance polyurethane pressure-sensitive adhesive in a PET protective film according to any one of claims 1-8, characterized in that: the polyurethane pressure-sensitive adhesive is evenly coated on a 50-60 μm thick PET base film On the corona surface, put the PET base film in an oven at 80-100°C for 5-10 minutes until the glue surface is dry, control the thickness of the dry glue to 10±1μm, and then cover the glue surface with a release film with a thickness of 50μm, and Place it in an oven at 40-50°C for 5 days and set aside.
  11. 根据权利要求1-8任一所述的一种高性能聚氨酯压敏胶在电器、汽车、液晶面板、通讯产品、计算机和消费电子产品中的用途。Use of a high-performance polyurethane pressure-sensitive adhesive according to any one of claims 1-8 in electrical appliances, automobiles, liquid crystal panels, communication products, computers and consumer electronics.
PCT/CN2022/116014 2021-12-07 2022-08-31 High-performance polyurethane pressure-sensitive adhesive, preparation method therefor, and application thereof WO2023103480A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111483032.8A CN114015405B (en) 2021-12-07 2021-12-07 High-performance polyurethane pressure-sensitive adhesive and preparation method and application thereof
CN202111483032.8 2021-12-07

Publications (1)

Publication Number Publication Date
WO2023103480A1 true WO2023103480A1 (en) 2023-06-15

Family

ID=80067958

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/116014 WO2023103480A1 (en) 2021-12-07 2022-08-31 High-performance polyurethane pressure-sensitive adhesive, preparation method therefor, and application thereof

Country Status (2)

Country Link
CN (1) CN114015405B (en)
WO (1) WO2023103480A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114015405B (en) * 2021-12-07 2023-04-07 襄阳三沃航天薄膜材料有限公司 High-performance polyurethane pressure-sensitive adhesive and preparation method and application thereof
CN115716904A (en) * 2022-11-28 2023-02-28 广州市斯洛柯高分子聚合物有限公司 Organic silicon modified bio-based polyurethane, preparation method thereof and synthetic leather containing organic silicon modified bio-based polyurethane

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102633983A (en) * 2012-05-18 2012-08-15 江西省科学院应用化学研究所 Preparation method for siloxane-terminated organosilicon block polyurethane prepolymer
KR20130086962A (en) * 2012-01-26 2013-08-05 조광호 Low-friction anti-fouling paints and low-friction buoy
CN103640293A (en) * 2013-11-27 2014-03-19 常熟市富邦胶带有限责任公司 Mobile-phone film with pu (Polyurethane) coating layer
CN104232004A (en) * 2014-09-26 2014-12-24 南京汇鑫光电材料有限公司 Polyurethane pressure-sensitive adhesive composition and preparation method and application thereof
CN104356342A (en) * 2014-11-04 2015-02-18 佛山市功能高分子材料与精细化学品专业中心 Organic silicon modified waterborne polyurethane leather coating agent and preparation method
CN105348469A (en) * 2015-12-15 2016-02-24 山东北方现代化学工业有限公司 Heat resistant waterproof high strength polyurethane adhesive and preparing method thereof
JP2016117827A (en) * 2014-12-19 2016-06-30 ヘンケルジャパン株式会社 Urethane pressure-sensitive adhesive
CN105837773A (en) * 2016-04-15 2016-08-10 武汉赫斯特涂层材料股份有限公司 Preparation method of double-modified hyperbranched waterborne polyurethane emulsion with silicone and renewable vegetable oil
CN106753169A (en) * 2016-08-23 2017-05-31 中山市鼎立森电子材料有限公司 A kind of mono-component polyurethane diaphragm pressure sensitive adhesive and its synthesis technique
CN107502275A (en) * 2017-09-27 2017-12-22 安徽大松树脂有限公司 A kind of fire-retardant antistripping adhesive for polyurethane
CN108779379A (en) * 2016-06-14 2018-11-09 汉高股份有限及两合公司 urethane adhesive
CN109777338A (en) * 2018-12-25 2019-05-21 三友（天津）高分子技术有限公司 High-intensitive high elongation at tear monocomponent polyurethane adhesive and preparation method
CN110885550A (en) * 2019-11-29 2020-03-17 东莞市吉鑫高分子科技有限公司 Organic silicon modified thermoplastic polyurethane elastomer and preparation method thereof
CN111777969A (en) * 2020-06-30 2020-10-16 浙江鑫钰新材料有限公司 Organic silicon modified polyurethane conductive adhesive
US20200362212A1 (en) * 2017-09-20 2020-11-19 Sika Technology Ag Compositions based on silane-terminated polymers with improved adhesion on thermoplastics
CN114015405A (en) * 2021-12-07 2022-02-08 襄阳三沃航天薄膜材料有限公司 High-performance polyurethane pressure-sensitive adhesive and preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110050444A (en) * 2008-09-05 2011-05-13 아사히 가라스 가부시키가이샤 Adhesive material, adhesive sheet and use of same
JP6915291B2 (en) * 2017-02-14 2021-08-04 東洋インキＳｃホールディングス株式会社 Surface protection adhesive and surface protection sheet
CN108251041A (en) * 2018-01-31 2018-07-06 有行鲨鱼（上海）科技股份有限公司 A kind of high-performance strength instant glue

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130086962A (en) * 2012-01-26 2013-08-05 조광호 Low-friction anti-fouling paints and low-friction buoy
CN102633983A (en) * 2012-05-18 2012-08-15 江西省科学院应用化学研究所 Preparation method for siloxane-terminated organosilicon block polyurethane prepolymer
CN103640293A (en) * 2013-11-27 2014-03-19 常熟市富邦胶带有限责任公司 Mobile-phone film with pu (Polyurethane) coating layer
CN104232004A (en) * 2014-09-26 2014-12-24 南京汇鑫光电材料有限公司 Polyurethane pressure-sensitive adhesive composition and preparation method and application thereof
CN104356342A (en) * 2014-11-04 2015-02-18 佛山市功能高分子材料与精细化学品专业中心 Organic silicon modified waterborne polyurethane leather coating agent and preparation method
JP2016117827A (en) * 2014-12-19 2016-06-30 ヘンケルジャパン株式会社 Urethane pressure-sensitive adhesive
CN105348469A (en) * 2015-12-15 2016-02-24 山东北方现代化学工业有限公司 Heat resistant waterproof high strength polyurethane adhesive and preparing method thereof
CN105837773A (en) * 2016-04-15 2016-08-10 武汉赫斯特涂层材料股份有限公司 Preparation method of double-modified hyperbranched waterborne polyurethane emulsion with silicone and renewable vegetable oil
CN108779379A (en) * 2016-06-14 2018-11-09 汉高股份有限及两合公司 urethane adhesive
CN106753169A (en) * 2016-08-23 2017-05-31 中山市鼎立森电子材料有限公司 A kind of mono-component polyurethane diaphragm pressure sensitive adhesive and its synthesis technique
US20200362212A1 (en) * 2017-09-20 2020-11-19 Sika Technology Ag Compositions based on silane-terminated polymers with improved adhesion on thermoplastics
CN107502275A (en) * 2017-09-27 2017-12-22 安徽大松树脂有限公司 A kind of fire-retardant antistripping adhesive for polyurethane
CN109777338A (en) * 2018-12-25 2019-05-21 三友（天津）高分子技术有限公司 High-intensitive high elongation at tear monocomponent polyurethane adhesive and preparation method
CN110885550A (en) * 2019-11-29 2020-03-17 东莞市吉鑫高分子科技有限公司 Organic silicon modified thermoplastic polyurethane elastomer and preparation method thereof
CN111777969A (en) * 2020-06-30 2020-10-16 浙江鑫钰新材料有限公司 Organic silicon modified polyurethane conductive adhesive
CN114015405A (en) * 2021-12-07 2022-02-08 襄阳三沃航天薄膜材料有限公司 High-performance polyurethane pressure-sensitive adhesive and preparation method and application thereof

Also Published As

Publication number Publication date
CN114015405A (en) 2022-02-08
CN114015405B (en) 2023-04-07

Similar Documents

Publication Publication Date Title
WO2023103480A1 (en) High-performance polyurethane pressure-sensitive adhesive, preparation method therefor, and application thereof
TWI642542B (en) Antistatic surface protection film
TWI612124B (en) Adhesive film and surface protection film
CN106661402B (en) Adhesive composition for optical film, adhesive layer, adhesive optical film and display device
TWI648363B (en) Adhesive composition and surface protection film
US20130233485A1 (en) Reactive conductive pressure-sensitive adhesive tape
EP2557135A2 (en) Adhesive composition, adhesive sheet, and touch panel
WO2012091283A2 (en) Adhesive composition for polarizer, and polarizer having same
TWI665277B (en) Adhesive composition and surface protection film
CN106398562A (en) Surface protective film for polarizing plate, polarizing plate and method for manufacturing polarizing plate
KR20120038633A (en) Adhesive composition, polarizing plate and liquid crystal display device comprising the same
KR20170115197A (en) Adhesive film
CN117050696A (en) Modified polyacrylate pressure-sensitive adhesive for folding adhesive tape and preparation method thereof
CN107001889A (en) Adhesion agent composition and adhesive tape
CN110527453A (en) The bonding sheet based on acrylic acid series copolymer for 5G antenna processing procedure
TWI782914B (en) Releasing film
CN113480688B (en) Solvent type acrylic resin and application thereof in battery wrapping pressure-sensitive adhesive tape
KR20230047165A (en) Reinforcing film, optical member and electronic member
CN111909649B (en) Adhesive, solar cell back sheet and solar cell
JP7030269B2 (en) Adhesives and adhesive sheets
WO2023007947A1 (en) Mold release film and method for manufacturing semiconductor package
WO2022215486A1 (en) Electroconductive composition
KR20230047162A (en) Reinforcing film, optical member and electronic member
KR101591106B1 (en) Pressure-sensitive adhesive composition for electronic components
KR20230047164A (en) Reinforcing film, optical member and electronic member

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22902911

Country of ref document: EP

Kind code of ref document: A1