CN110835513B - Double-component polyurethane adhesive - Google Patents
Double-component polyurethane adhesive Download PDFInfo
- Publication number
- CN110835513B CN110835513B CN201810933802.6A CN201810933802A CN110835513B CN 110835513 B CN110835513 B CN 110835513B CN 201810933802 A CN201810933802 A CN 201810933802A CN 110835513 B CN110835513 B CN 110835513B
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- CN
- China
- Prior art keywords
- component
- polyurethane adhesive
- polyol
- polyoxypropylene
- molecular weight
- Prior art date
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 51
- 239000000853 adhesive Substances 0.000 title claims abstract description 50
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 229920005862 polyol Polymers 0.000 claims abstract description 69
- 150000003077 polyols Chemical class 0.000 claims abstract description 67
- -1 polyoxypropylene Polymers 0.000 claims abstract description 51
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 48
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims abstract description 37
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims abstract description 37
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 23
- 239000005025 cast polypropylene Substances 0.000 claims description 25
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 13
- 150000002009 diols Chemical class 0.000 claims description 12
- 229920005906 polyester polyol Polymers 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000009459 flexible packaging Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 13
- 239000003292 glue Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- WOVNROWPOFTJPT-UHFFFAOYSA-N 2,3-diisocyanato-2,3-dimethylbutane Chemical compound O=C=NC(C)(C)C(C)(C)N=C=O WOVNROWPOFTJPT-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a two-component polyurethane adhesive, which adopts polyoxypropylene polyol and bisphenol A initiated polyether polyol to be matched with organic isocyanate for use, so that the adhesive has good leveling property, ink matching property, low friction coefficient property, adhesive force and heat resistance, and particularly has excellent adhesive property to a BOPP/CPP composite structure.
Description
Technical Field
The invention relates to a two-component polyurethane adhesive, in particular to a two-component polyurethane adhesive for soft package compounding, and particularly relates to a polyurethane adhesive with excellent adhesion to a BOPP/CPP composite structure.
Background
The double-component polyurethane adhesive is an important classification of polyurethane adhesives, generally comprises two components of isocyanate compounds and hydroxyl compounds, and the final bonding effect is realized through the mixing reaction of the isocyanate compounds and the hydroxyl compounds. This type of adhesive has a wide adjustable range of properties and is therefore widely used in many fields.
An important field of application for two-component polyurethane adhesives is flexible packaging. The traditional double-component polyurethane adhesive for flexible packaging is a solvent type product, commonly called dry type composite adhesive, and has the disadvantages of high energy consumption in the production process, high potential safety hazard and serious environmental pollution due to the large use of organic solvents such as ethyl acetate and the like. The solvent-free double-component polyurethane adhesive technology is adopted, so that the problems are well solved. Since 2012, the development of domestic solvent-free two-component polyurethane adhesives is rapid, and the market capacity is increased to 4-5 ten thousand tons/year. However, with the increase of market demand, the solvent-free technology has many limitations, and a more prominent contradiction is that the compatibility is limited, and the compatibility is particularly low on some structures, for example, on a biaxially oriented polypropylene film (BOPP)/cast polypropylene film (CPP) composite structure, the composite fastness is usually only 0.2-0.5N/15mm, which is obviously lower than the national standard (0.6N/15mm), and becomes an industry pain point.
Patent CN106675499A discloses a solvent-free two-component polyurethane cooking glue and a preparation method thereof, and although the cooking performance is improved by the technology, the problem of low composite fastness on a special structure is not solved, and the problem that the friction coefficient is obviously increased due to the system is solved.
Patent CN101597470A discloses a solvent-free two-component polyurethane adhesive and a preparation method thereof, and the technology obtains better low-temperature coating performance by reducing system viscosity; however, the viscosity of 2000-5000mPa.s is still high, which is unfavorable for the final transparency of the composite product and is limited by the system characteristics, and the composite fastness (peel strength) is not optimistic on the BOPP/CPP composite structure.
Therefore, it is desirable to provide an adhesive having good overall properties, especially excellent adhesion to BOPP/CPP composite structures.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a two-component polyurethane adhesive which has excellent comprehensive properties including good leveling property, good ink matching property, low friction coefficient property, adhesive force and heat resistance, and particularly has excellent adhesion to a BOPP/CPP composite structure.
In order to solve the technical problems, the technical scheme of the two-component polyurethane adhesive provided by the invention is as follows:
a two-component polyurethane adhesive comprises a component A and a component B;
the component A is an organic isocyanate component, and the component B comprises polyoxypropylene polyol B1 and bisphenol A initiated polyether polyol B2; the propylene oxide polyol B1 and the bisphenol A initiated polyether polyol B2 were different.
The polyoxypropylene polyol B1 is a polyether polyol obtained by polymerizing a polyol as an initiator and propylene oxide as a polymerization monomer. The initiator of the polyoxypropylene polyol B1 can be any polyol commonly used in the art, and has a functionality of 2-4, preferably 2-3, examples of which include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, butanediol, pentanediol, pentaerythritol, and the like, and such polyols can be used alone or in combination. It should be noted that the initiator of the polyoxypropylene polyol B1 does not include bisphenol A. The acquisition route of the polyoxypropylene polyol B1 can be synthesized by a technical scheme well known in the art, and can also be obtained by commercial procurement.
The average molecular weight of the component B is 1000-4000, preferably 1500-2500.
The polypropylene oxide polyol B1 provides good adhesion due to better affinity and wettability with polyolefin films BOPP and CPP. Wherein, the polypropylene oxide polyol with bifunctionality provides good flexibility for the system, and the polypropylene oxide polyol with functionality more than 2 provides a crosslinking point for the system; preferably, the difunctional and functionality of the polyoxypropylene polyols of greater than 2 act synergistically to provide the appropriate cohesive energy to the system.
In a preferred example, the polyoxypropylene polyol B1 comprises a polyoxypropylene diol and a polyoxypropylene triol; more preferably, the molecular weight of the polyoxypropylene diol is 400-8000, preferably 2000-4000, and the molecular weight of the polyoxypropylene triol is 400-8000, preferably 400-3000; still more preferably, the mass ratio of the polyoxypropylene diol to the polyoxypropylene triol is 1: 0.1 to 2, preferably 1: 0.2 to 1. The polypropylene oxide polyol B1 has better affinity and wettability with polyolefin films BOPP and CPP, so that the adhesion force on the structure is good. The polypropylene oxide glycol provides good flexibility for the system; the polyoxypropylene triol provides a certain crosslinking density, and the control of the proportion of the polyoxypropylene triol and the crosslinking density can endow the adhesive layer with proper toughness and strength, so that the adhesive force is further improved.
The bisphenol A initiated polyether polyol B2 is a polyether polyol generated by polymerization of bisphenol A as an initiator and propylene oxide and/or ethylene oxide as a polymerization monomer. Preferably, the bisphenol A initiated polyether polyol B2 has a molecular weight of 300-1500, preferably 400-900. Because the polyether polyol B2 contains a rigid group bisphenol A structure, the thermal stability is good, the problem of insufficient heat resistance of the polyether polyol B1 can be solved by adding the reaction system, and the steaming resistance of the system is effectively improved.
In a preferred embodiment, the mass ratio of polyoxypropylene polyol B1 to bisphenol A initiated polyether polyol B2 is 1: 0.1 to 0.5, preferably 1: 0.11 to 0.3.
The component B may further comprise polyester polyol, which is commercially available, or polyester polyol obtained by condensation polymerization of polyol and polybasic acid commonly used in the art, examples of the commonly used polyol include, but are not limited to, ethylene glycol, propylene glycol, methyl propylene glycol, butylene glycol, trimethylolpropane, etc., such polyols may be used alone or in combination, examples of the commonly used polybasic acid include, but are not limited to, adipic acid, sebacic acid, phthalic anhydride, terephthalic acid, isophthalic acid, etc., such polybasic acid may be used alone or in combination.
The component B can also comprise polylactones, which can be obtained by commercial purchase or by conventional preparation methods in the field, and common lactones for preparing polylactones include but are not limited to gamma-butyrolactone, epsilon-caprolactone and the like, and the lactones can be used singly or in combination.
The component B can also comprise polycarbonate polyol, and the polycarbonate polyol can be obtained by commercial purchase or preparation method commonly used in the field.
The B component may also comprise bio-based polyols including, but not limited to, castor oil, soy oil polyols, olive oil, and modified bio-based polyols, among others, which may be used alone or in combination.
The B component may also contain optional additives such as coupling agents, antioxidants, wetting agents, leveling agents, fillers, catalysts, and the like.
In a preferred embodiment, the B component does not contain a bio-based polyol. This is because the addition of bio-based polyol has a significant effect on the coefficient of friction of Polyethylene (PE) films, which in turn limits the compatibility of the adhesive on PE structures.
In a preferred embodiment, the component B does not comprise a polyester polyol. The addition of polyester polyol can reduce the ink matching of the system, and further cause the compatibility of the adhesive on an aluminum-plated film structure to be reduced.
The component A is an organic isocyanate component, and refers to isocyanate compounds such as organic isocyanate with isocyanate end groups, modified isocyanate, isocyanate prepolymer and the like, and the obtaining route can be prepared by adopting a method commonly used in the field and can also be obtained by commercial purchase, such as WANNATE6092A and the like produced by Wanhua chemical industry.
Preferably, the component A has an NCO content of 12-20 wt%, preferably 14-17 wt%, a functionality of 2-4, preferably 2-2.5, and a viscosity of 1000-4000 mPa.s, preferably 1500-3000 mPa.s, at 25 ℃.
In a preferred embodiment, the A component is an isocyanate prepolymer obtained by reacting an organic isocyanate A1 with a polyol A2. The organic isocyanate a1 may be selected from isocyanates commonly used in the art, and examples thereof include, but are not limited to, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenylmethane Polyisocyanate (PMDI), 1, 5-Naphthalene Diisocyanate (NDI), Hexamethylene Diisocyanate (HDI), methylcyclohexyl diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), tetramethyldimethylene diisocyanate (TMXDI), and the like, and polymers of such isocyanates, and the above-mentioned isocyanates and/or isocyanate polymers may be used alone or in combination. The polyol a2 may be selected from polyols commonly used in the art, and examples thereof include, but are not limited to, polyether polyols, polyester polyols, polycaprolactone polyols, polycarbonate polyols, bio-based polyols, and the like, and such polyols may be used alone or in combination.
In a preferred example, the organic isocyanate a1 is diphenylmethane diisocyanate (MDI) and the polyol a2 is a polyester polyol and/or a polyether polyol.
The parameters of functionality, molecular weight, dosage and the like of the polyester polyol and the polyether polyol used for synthesizing the isocyanate prepolymer in the component A can adopt the parameters commonly used in the field, and do not influence the implementation of the invention.
In a preferred embodiment, based on the total mass of the component a:
the using amount of the organic isocyanate A1 is 25-70%, preferably 50-60%;
the amount of the polyester polyol used for synthesizing the isocyanate prepolymer in the component A is 5-20%, preferably 10-15%;
the amount of the polyether polyol used for synthesizing the isocyanate prepolymer in the component A is 20-50%, preferably 25-40%.
The mass ratio of the component A to the component B is 1: 0.4 to 0.9, preferably 1: 0.5 to 0.7.
The preparation method of the two-component polyurethane adhesive can adopt a preparation method commonly used in the field, and the implementation of the invention is not influenced.
In a preferred embodiment, when the component A is obtained by synthesis, the preparation method comprises the following steps: adding the raw materials of the component A into a reactor, continuously stirring for reaction, wherein the reaction temperature is 60-90 ℃, preferably 70-80 ℃, and obtaining the component A after the reaction.
In a preferred embodiment, the component B is prepared by the following steps: and adding the raw materials of the component B into a reactor, and uniformly stirring at 50-80 ℃, preferably 60-70 ℃ to obtain the component B.
The two-component polyurethane adhesive can be used for adhering membranous or layered substrates, particularly for adhering soft layered substrates in flexible packages; in particular, the adhesive is excellent in adhesion to a biaxially oriented polypropylene film (BOPP) and a cast polypropylene film (CPP).
The application method of the two-component polyurethane adhesive can adopt the application method commonly used in the field, for example, the component A and the component B are uniformly mixed and then coated on a substrate needing to be bonded, and then the substrate is attached and cured; or firstly coating one component on a substrate needing to be bonded, then coating the other component on the substrate, and then laminating and curing the substrate, and the like.
The two-component polyurethane adhesive disclosed by the invention has excellent comprehensive properties including good leveling property, good ink matching property, low friction coefficient, excellent adhesive force and heat resistance, and can be suitable for bonding of various materials, especially for bonding of nonpolar materials, such as BOPP/CPP compounding.
Detailed Description
The raw materials used in the examples and comparative examples are as follows:
polyol-1: DL2000D, polyoxypropylene diol, molecular weight 2000, manufactured by Shandong Lanxingdong GmbH;
polyol-2: DL3000D, polyoxypropylene diol, molecular weight 3000, manufactured by Shandong Lanxingdong GmbH;
polyol-3: DL4000D, polyoxypropylene glycol, molecular weight 4000, santong blue star east da ltd;
polyol-4: DMN400, polyoxypropylene triol, molecular weight 400, manufactured by Zibode letter Federal;
polyol-5: DMN1000, polyoxypropylene triol, molecular weight 1000, manufactured by Zibode letter Federal;
polyol-6: DEP560D, polyoxypropylene triol, molecular weight 3000, manufactured by Zibode Federal;
polyol-7: HMP-532B, bisphenol A initiated polyether polyol, molecular weight 400, produced by Huangjiang Royal technologies, Inc.;
polyol-8: BPA-8.5EO, bisphenol A initiated polyether polyol, molecular weight 600, produced by Huangjiang Royal technologies;
polyol-9: HMP-533B, bisphenol A initiated polyether polyol, molecular weight 900, produced by Huangjiang Huangma science and technology;
polyol-10: castor oil, industrial grade one;
polyol-11: DL400, polyoxypropylene diol, molecular weight 400, produced by Shandong Lanxingdao Co., Ltd;
polyol-12: DL1000D, polyoxypropylene diol, molecular weight 1000, available from Shandong Lanxingdong Co., Ltd;
polyol-13: XCP-2000N, polyester polyol, molecular weight 2000, available from Asahi Sichuan chemical (Suzhou) Co., Ltd.;
polyol-14: XCP-355, polyester polyol, MW 1000, manufactured by Asahi Sichuan chemical (Suzhou) Co., Ltd;
organic isocyanate:
MDI-100, NCO% ═ 33.5 wt%, viscosity 4.7mPa.s at 50 ℃, produced by Wanhua chemical group Limited;
organic isocyanate:
6092A, NCO% ═ 14-18 wt%, viscosity 1200mPa.s at 25 ℃, produced by Wanhua chemical group Limited;
organic isocyanate-1: prepared by a laboratory, wherein the NCO percent is 14 percent by weight, the viscosity is 3000mPa.s at 25 ℃, and the formula is shown in table 1;
organic isocyanate-2: prepared by a laboratory, the NCO percent is 17 percent by weight, the viscosity is 1500mPa.s at 25 ℃, and the formula is shown in table 1.
The raw materials used for organic isocyanate-1 and organic isocyanate-2 are listed in Table 1, and the preparation method comprises the following steps: according to the types and the use amounts shown in the table 1, the raw materials are added into a reactor and stirred for reaction, the reaction temperature is 75 ℃, the reaction is finished within 3 hours, and then the materials are discharged.
The preparation method of the component B comprises the following steps: according to the types and the dosage shown in the table 2, the component B corresponding to each raw material is added into a reactor, the temperature is raised to 65 ℃, and the mixture is stirred for 2 hours and then discharged.
TABLE 1 (parts by mass)
TABLE 2 (parts by mass)
Preparation of performance test samples:
1. after the prepared component A and the component B are uniformly mixed according to the proportion in the table 1, respectively compounding the structures of BOPP/CPP, PA (nylon)/PE (polyethylene) and BOPP/VMPET (vacuum aluminum plated polyethylene terephthalate);
2. and curing the compounded sample piece at 45 ℃ for 48 hours to obtain a performance test sample piece.
Respectively testing the peel strength, boiling resistance, friction coefficient, ink matching property and leveling property of the performance test sample wafer:
the test standards for peel strength are GB/T8808-1988;
the test standard of the friction coefficient is GB/T10006-1988;
the boiling resistance test method comprises the following steps: placing the performance test sample wafer in 100 ℃ water to be boiled for 40 minutes, and then testing the peel strength according to the peel strength test standard;
the testing method of the ink matching performance comprises the following steps: visually observing whether the printing ink is dissolved or not;
the leveling property test method comprises the following steps: visually observing whether the glue is aggregated to form glue dots
The results of the BOPP/CPP structure peel strength test are shown in Table 3.
TABLE 3
| Composite structure | Peel strength (N/15mm) | |
| Example 1 | BOPP/CPP | 0.92 |
| Example 2 | BOPP/CPP | 0.89 |
| Example 3 | BOPP/CPP | 0.88 |
| Example 4 | BOPP/CPP | 0.91 |
| Example 5 | BOPP/CPP | 0.90 |
| Comparative example 1 | BOPP/CPP | 0.52 |
| Comparative example 2 | BOPP/CPP | 0.83 |
| Comparative example 3 | BOPP/CPP | 0.49 |
| Comparative example 4 | BOPP/CPP | 0.37 |
Table 3 the results show: in examples 1-5, the peel strength of the BOPP/CPP structure is obviously higher than 0.6N/15mm, and the BOPP/CPP structure meets the national standard requirements.
The results of the PA/PE construction water boil performance and coefficient of friction tests are listed in table 4.
TABLE 4
Table 4 the results show: examples 1 to 5 were excellent in both the water boiling property and the friction coefficient, and it was demonstrated that bisphenol A polyoxypropylene ether had a significant effect on the heat resistance, while polyoxypropylene polyol and bisphenol A polyoxypropylene ether were excellent in the friction coefficient.
The ink match and leveling test results for the BOPP/VMPET structures are listed in Table 5.
TABLE 5
| Composite structure | Ink compatibility | Leveling property | |
| Example 1 | BOPP/VMPET | No dissolution, excellence | No glue spot, excellence |
| Example 2 | BOPP/VMPET | No dissolution, excellence | No glue spot, excellence |
| Example 3 | BOPP/VMPET | No dissolution, excellence | No glue spot, excellence |
| Example 4 | BOPP/VMPET | No dissolution, excellence | No glue spot, excellence |
| Example 5 | BOPP/VMPET | No dissolution, excellence | No glue spot, excellence |
| Comparative example 1 | BOPP/VMPET | No dissolution, excellence | No glue spot, excellence |
| Comparative example 2 | BOPP/VMPET | No dissolution, excellence | No glue spot, excellence |
| Comparative example 3 | BOPP/VMPET | No dissolution, excellence | No glue spot, excellence |
| Comparative example 4 | BOPP/VMPET | Dissolution, poor | A small amount of glue dots, good |
Table 5 the results show: examples 1 to 5 were excellent in both ink compatibility and leveling property.
Claims (19)
1. A two-component polyurethane adhesive is characterized by comprising a component A and a component B;
the component A is an organic isocyanate component, and the component B comprises polyoxypropylene polyol B1 and bisphenol A initiated polyether polyol B2; the propylene oxide polyol B1 and the bisphenol A initiated polyether polyol B2 are different; the polyoxypropylene polyol B1 comprises a polyoxypropylene diol and a polyoxypropylene triol; the mass ratio of the polyoxypropylene diol to the polyoxypropylene triol is 1: 0.1 to 2; the polyoxypropylene polyol B1 is a polyether polyol obtained by polymerizing a polyol as an initiator and propylene oxide as a polymerization monomer.
2. The polyurethane adhesive as claimed in claim 1, wherein the average molecular weight of the component B is 1000-4000.
3. The polyurethane adhesive as claimed in claim 2, wherein the average molecular weight of the component B is 1500-.
4. The polyurethane adhesive according to claim 1, wherein the polyoxypropylene diol has a molecular weight of 400-8000, and the polyoxypropylene triol has a molecular weight of 300-8000.
5. The polyurethane adhesive according to claim 4, wherein the polyoxypropylene diol has a molecular weight of 2000-4000 and the polyoxypropylene triol has a molecular weight of 400-3000.
6. The polyurethane adhesive according to claim 1, wherein the mass ratio of the polyoxypropylene diol to the polyoxypropylene triol is 1: 0.2 to 1.
7. The polyurethane adhesive of any one of claims 1 to 6, wherein the bisphenol A initiated polyether polyol B2 has a molecular weight of 300 to 1500.
8. The polyurethane adhesive of claim 7, wherein the bisphenol A initiated polyether polyol B2 has a molecular weight of 400 to 900.
9. The polyurethane adhesive according to any one of claims 1 to 6, wherein the mass ratio of the polyoxypropylene polyol B1 to the bisphenol A initiated polyether polyol B2 is 1: 0.1 to 0.5.
10. The polyurethane adhesive of claim 9, wherein the mass ratio of the polyoxypropylene polyol B1 to the bisphenol a-initiated polyether polyol B2 is 1: 0.11 to 0.3.
11. The polyurethane adhesive according to any one of claims 1 to 6, wherein the component A has an NCO content of 12 to 20 wt%, a functionality of 2 to 4, and a viscosity of 1000 to 4000 mPa-s at 25 ℃.
12. The polyurethane adhesive according to claim 11, wherein the component A has an NCO content of 14 to 17 wt%, a functionality of 2 to 2.5, and a viscosity of 1500 to 3000mPa · s at 25 ℃.
13. The polyurethane adhesive according to any one of claims 1 to 6, wherein the A component is prepared from the following raw materials: based on the total mass of the component A,
the using amount of the organic isocyanate A1 is 25-70%;
the using amount of the polyester polyol is 5-20%;
the using amount of the polyether polyol is 20-50%.
14. The polyurethane adhesive according to claim 13, wherein the component A is selected from the group consisting of, based on the total mass of the component A,
the using amount of the organic isocyanate A1 is 50-60%;
the using amount of the polyester polyol is 10-15%;
the using amount of the polyether polyol is 25-40%.
15. The polyurethane adhesive according to any one of claims 1 to 6, wherein the mass ratio of the component A to the component B is 1: 0.4 to 0.9.
16. The polyurethane adhesive according to claim 15, wherein the mass ratio of the component a to the component B is 1: 0.5 to 0.7.
17. The polyurethane adhesive of any one of claims 1-16 for bonding film-like or layered substrates.
18. The use of the polyurethane adhesive according to claim 17 for the adhesion of flexible laminar substrates in flexible packaging.
19. The use according to claim 18, said polyurethane adhesive being used for the bonding of biaxially oriented polypropylene film and/or cast polypropylene film.
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