CN112625638A - Universal coating adhesive and preparation method thereof - Google Patents
Universal coating adhesive and preparation method thereof Download PDFInfo
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- CN112625638A CN112625638A CN202011496151.2A CN202011496151A CN112625638A CN 112625638 A CN112625638 A CN 112625638A CN 202011496151 A CN202011496151 A CN 202011496151A CN 112625638 A CN112625638 A CN 112625638A
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- polyester polyol
- parts
- polyol
- coating adhesive
- acrylic resin
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- 239000011248 coating agent Substances 0.000 title claims abstract description 82
- 238000000576 coating method Methods 0.000 title claims abstract description 82
- 239000000853 adhesive Substances 0.000 title claims abstract description 54
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 135
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 62
- 229920000570 polyether Polymers 0.000 claims abstract description 62
- 229920005862 polyol Polymers 0.000 claims abstract description 46
- 150000003077 polyols Chemical class 0.000 claims abstract description 46
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 38
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 38
- 239000004970 Chain extender Substances 0.000 claims abstract description 32
- 239000012948 isocyanate Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 21
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 20
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 19
- 239000003292 glue Substances 0.000 claims abstract description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 58
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 229910021485 fumed silica Inorganic materials 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- -1 aromatic isocyanate Chemical class 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002023 wood Substances 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 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 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 238000012935 Averaging Methods 0.000 description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- 239000004575 stone Substances 0.000 description 4
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004831 Hot glue Substances 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- WMNWJTDAUWBXFJ-UHFFFAOYSA-N 3,3,4-trimethylheptane-2,2-diamine Chemical compound CCCC(C)C(C)(C)C(C)(N)N WMNWJTDAUWBXFJ-UHFFFAOYSA-N 0.000 description 1
- BPINJMQATUWTID-UHFFFAOYSA-N 3,3-dimethylpentane-2,2-diamine Chemical compound CCC(C)(C)C(C)(N)N BPINJMQATUWTID-UHFFFAOYSA-N 0.000 description 1
- OMAUSUKGZFZKBA-UHFFFAOYSA-N 5,5,6-trimethylheptane-1,6-diamine Chemical compound CC(C)(N)C(C)(C)CCCCN OMAUSUKGZFZKBA-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004017 vitrification Methods 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
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of coating glue, in particular to universal coating glue and a preparation method thereof. The raw materials of the coating adhesive comprise, by weight, 15-30 parts of polyether polyol, 10-20 parts of acrylic resin, 35-80 parts of polyester polyol, 0.01-0.05 part of a defoaming agent, 5-15 parts of a polyurethane elastomer, 0-5 parts of a filler, 5-10 parts of a chain extender, 10-20 parts of isocyanate and 0.01-0.1 part of a catalyst. The coating adhesive can meet the coating application of various base materials, has good initial strength and later strength, and solves the problems of adhesion to wood materials, wood plastics, aluminum materials and the like and initial adhesion of thick film materials.
Description
Technical Field
The invention relates to the technical field of coating glue, in particular to universal coating glue and a preparation method thereof.
Background
In the field of household building materials, a process of bonding a specific irregular section and a film material with a certain pattern on the surface is called coating, and the coated material is common such as indoor wall boards, storage cabinets, door pocket lines and the like. Currently, polyurethane hot melt adhesives are mostly selected and applied to the coating industry in the market. Because the coated base materials are various in types, such as wood-plastic wall boards, stone-plastic lines, plastic steel, density boards, aluminum alloys, solid wood and the like, and the surface materials such as PVC films, PP films, veneers, CPL and the like, the problem is also faced, namely, different types of coating glue are required for coating different base materials, and the characteristics of various glues are different, so that the coating on the same glue supply equipment has many troubles.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a general-purpose coating adhesive, and the raw materials of the coating adhesive comprise, by weight, 15-30 parts of polyether polyol, 10-20 parts of acrylic resin, 35-80 parts of polyester polyol, 0.01-0.05 part of a defoaming agent, 5-15 parts of a polyurethane elastomer, 0-5 parts of a filler, 5-10 parts of a chain extender, 10-20 parts of isocyanate and 0.01-0.1 part of a catalyst.
As a preferable technical scheme of the invention, the functionality of the polyether polyol is 2-6, and the hydroxyl value is 19-56 mg/g.
In a preferred embodiment of the present invention, the acrylic resin is a polar acrylic resin.
As a preferred embodiment of the present invention, the polyester polyol includes liquid polyester polyol, crystalline polyester polyol, and amorphous polyester polyol.
As a preferred technical solution of the present invention, the polyester polyol further comprises a high molecular weight polyester polyol; wherein the weight ratio of the high molecular weight polyester polyol to the crystalline polyester polyol is 1: 2.
as a preferable technical scheme of the invention, the filler is at least one of talcum powder, fumed silica and calcium carbonate.
As a preferable technical scheme, the chain extender is an aromatic chain extender.
In a preferred embodiment of the present invention, the isocyanate is an aromatic isocyanate.
As a preferable technical scheme of the invention, the catalyst is an organic amine catalyst. The second aspect of the invention provides a preparation method of a universal coating adhesive, which comprises the following steps:
(1) adding polyether glycol, acrylic resin, a defoaming agent and a filler into a reaction kettle A with a high-speed dispersion characteristic, adjusting the temperature to 130-150 ℃, melting for 2 hours, and vacuumizing and dehydrating for 30 minutes;
(2) adding polyester polyol and polyurethane elastomer into a reaction kettle B, regulating the temperature to 130-150 ℃, melting for 1-1.5 hours, and vacuumizing and dehydrating for 30 minutes;
(3) adding a proper amount of the mixture in the reaction kettle A into the reaction kettle B, and then vacuumizing, stirring and dehydrating for 1 hour at the temperature of 120-140 ℃;
(4) cooling to 100-;
(5) cooling to 70 ℃, adding isocyanate, reacting and defoaming for 1-2 hours under the condition of introducing nitrogen, wherein the temperature of the whole reaction process is 80-120 ℃;
(6) after the reaction is finished, adding a catalyst, discharging under the protection of nitrogen, and sealing and packaging to obtain the universal coating adhesive.
The invention has the following beneficial effects:
1. the coating adhesive is suitable for but not limited to wood-plastic materials, stone-plastic materials, wood materials, aluminum materials, mineral plates, or the materials subjected to surface treatment, and can be applied to bonding with PVC (polyvinyl chloride) film materials, PP (polypropylene) film materials, melamine composite film materials, paper and fabric surface materials in different forms;
2. according to the invention, the contents of polyester polyol, acrylic resin and a chain extender are reasonably controlled, so that the prepared coating adhesive has good initial strength and later strength;
3. the prepared coating adhesive is 100 percent of solid content, needs to be heated and melted to finish the gluing and coating, has the gluing temperature of 120-140 ℃, and is lower than the coating adhesive for high temperature of about 160 ℃ on the market;
4. the application process is simple and convenient, the viscosity smoothness of the coating adhesive is excellent, the coating is facilitated, the viscosity is 45000-80000mPa.s/120 ℃, and the requirement of high-speed coating line can be met, such as 70 m/min;
5. the coating adhesive has good heating stability, can be continuously heated for 48 hours at 110 ℃, has the viscosity change of not more than 2 times, and completely meets the use requirements of adhesive melting equipment of a pressure plate and an adhesive cylinder;
6. the coating adhesive has moderate softening point and moderate opening time, and can adapt to the environment temperature of 10-40 ℃;
7. the coating adhesive is used for coating the wood-plastic wallboard-PVC film, and after the curing is carried out for 24 hours, the 180-degree stripping force is greater than 45N/25 mm;
8. the coating glue of the invention coats the density board-CPL film, the glue applying amount is about 50 g/square meter, the invention can coat the plane material with the film thickness of about 30 threads, and the rebound phenomenon is avoided;
9. the coating adhesive disclosed by the invention coats the chromized aluminum alloy-PVC film, and after the film is cured for 24 hours, the film material breaking effect is achieved.
Detailed Description
The first aspect of the invention provides a universal coating adhesive, and the raw materials of the coating adhesive comprise, by weight, 15-30 parts of polyether polyol, 10-20 parts of acrylic resin, 35-80 parts of polyester polyol, 0.01-0.05 part of a defoaming agent, 5-15 parts of a polyurethane elastomer, 0-5 parts of a filler, 5-10 parts of a chain extender, 10-20 parts of isocyanate and 0.01-0.1 part of a catalyst.
Preferably, the raw materials of the coating rubber comprise, by weight, 26 parts of polyether polyol, 15 parts of acrylic resin, 59 parts of polyester polyol, 0.03 part of a defoaming agent, 9 parts of a polyurethane elastomer, 2.8 parts of a filler, 7.2 parts of a chain extender, 15 parts of isocyanate and 0.06 part of a catalyst.
Polyether polyols
The polyether polyol has a functionality of 2 to 6 and a hydroxyl value of 19 to 56 mgKOH/g.
Preferably, the polyether polyol has a functionality of 2-4 and a hydroxyl value of 28-56 mg KOH/g.
Further preferably, the polyether polyol is a mixture of a polyether polyol having a functionality of 2 and a hydroxyl value of 56mg KOH/g and a polyether polyol having a functionality of 4 and a hydroxyl value of 28mg KOH/g, wherein the weight ratio of the polyether polyol having a functionality of 2 and a hydroxyl value of 56mg KOH/g and the polyether polyol having a functionality of 4 and a hydroxyl value of 28mg KOH/g is 1: (2-3).
Further preferably, the weight ratio of the polyether polyol having a functionality of 2 and a hydroxyl value of 56mg KOH/g to the polyether polyol having a functionality of 4 and a hydroxyl value of 28mg KOH/g is 1: 2.5.
the polyether polyol is polyether 2020 polyether polyol with the functionality of 2 and the hydroxyl value of 56mg KOH/g, and the polyether polyol with the functionality of 4 and the hydroxyl value of 28mg KOH/g is polyether 4040, and is purchased from Spilaulification chemical engineering science and technology Co.
In the invention, the performance of the coating adhesive prepared by compounding polyether 2020 and polyether 4040 is better.
Acrylic resin
The acrylic resin is polar acrylic resin.
Preferably, the hydroxyl content of the polar acrylic resin is 0.5-3%, and the acid value is 0.5-10 mg KOH/g; more preferably, the polar acrylic resin has a hydroxyl group content of 0.16-2% and an acid value of 3-7 mg KOH/g.
Further preferably, the polar acrylic resin is amino acrylic resin and/or hydroxy acrylic resin; more preferably, the polar acrylic resin is a hydroxy acrylic resin.
The hydroxy acrylic resin in the invention is Setalux D A760 BA/X.
Polyester polyols
The polyester polyol comprises liquid polyester polyol, crystalline polyester polyol and amorphous polyester polyol, wherein the weight ratio of the polyester polyol to the crystalline polyester polyol to the amorphous polyester polyol is (2-4): (3-6): (1-3); further preferably, the weight ratio of the polyester polyol, the crystalline polyester polyol and the amorphous polyester polyol is 3: 5: 2.
preferably, the hydroxyl value of the liquid polyester polyol is 18-34 mg KOH/g; further preferably, the hydroxyl value of the liquid polyester polyol is 27-34 mg KOH/g.
Preferably, the glass transition temperature of the liquid polyester polyol is-30 to-10 ℃; further preferably, the glass transition temperature of the liquid polyester polyol is-30 ℃.
The liquid polyester polyol used in the present invention is the winning polyester polyol Dynacoll 7230.
Preferably, the hydroxyl value of the crystalline polyester polyol is 10-47 mg KOH/g; further preferably, the hydroxyl value of the crystalline polyester polyol is 27 to 34mg KOH/g.
Preferably, the weight average molecular weight of the crystalline polyester polyol is 2000-4000; further preferably, the weight average molecular weight of the crystalline polyester polyol is 3500.
The crystalline polyester polyol used in the present invention is the winning polyester polyol Dynacoll 7380.
Preferably, the hydroxyl value of the amorphous polyester polyol is 18-46 mg KOH/g; further preferably, the hydroxyl value of the amorphous polyester polyol is 31-39 mg KOH/g.
Preferably, the glass transition temperature of the amorphous polyester polyol is 20-50 ℃; further preferably, the amorphous polyester polyol has a glass transition temperature of 30 ℃.
The amorphous polyester polyol used in the present invention is the winning polyester polyol Dynacoll 7130.
In the system, the interaction of liquid polyester polyol, crystalline polyester polyol and amorphous polyester polyol is used, and the wettability of the system is increased, so that the finally synthesized coating adhesive has good initial adhesion.
More preferably, the polyester polyol further comprises a high molecular weight polyester polyol; wherein the weight ratio of the high molecular weight polyester polyol to the crystalline polyester polyol is 1: 2.
more preferably, the weight average molecular weight of the high molecular weight polyester polyol is 8000-30000; more preferably, the high molecular weight polyester polyol has the weight average molecular weight of 12000-25000; still more preferably, the high molecular weight polyester polyol has a weight average molecular weight of 20000.
Further preferably, the hydroxyl value of the high molecular weight polyester polyol is 4-16 mg KOH/g; more preferably, the hydroxyl value of the high molecular weight polyester polyol is 4-6 mg KOH/g.
The high molecular weight polyester polyol used in the present invention is purchased from hk-20000 of Jining HuaKai resin Co.
The applicant found that in the present application the initial strength of the coating paste is influenced by the addition of the polyether polyol, but the addition of a suitable amount of high molecular weight polyester polyol to the system may increase the initial strength of the coating paste to some extent, probably because the high molecular weight polyester polyol may, to some extent, improve some of the drawbacks of the initial rapid positioning of the polyether polyol due to the synergistic effect of the high molecular weight polyester polyol and the crystalline polyester polyol.
Defoaming agent
The defoamer is not limited and all defoamers suitable for use in polyurethane systems are suitable for use in the present system.
As the defoaming agent, BYK-065, BYK-021, BYK-088, BYK-067, BYK-051 and the like can be exemplified.
The defoaming agent used in the invention is BYK-021.
Polyurethane elastomer
The polyurethane elastomer is a thermoplastic polyurethane elastomer.
The thermoplastic polyurethane elastomer used in the present invention is Wanhua WHT-6232.
The thermoplastic polyurethane elastomer is added into the system, so that the system has better toughness and elasticity, the problem of low-temperature brittleness of the existing hot melt adhesive product is solved, and the low-temperature cohesiveness of the coating adhesive is improved.
Filler material
In order to reduce the cost of the moisture-curing coating adhesive, a certain amount of filler is added in the invention, and the performance of the coating adhesive can be improved to a certain extent by adding a certain amount of filler.
The filler is at least one of talcum powder, fumed silica and calcium carbonate.
Preferably, the filler is a mixture of fumed silica and calcium carbonate, wherein the weight ratio of fumed silica to calcium carbonate is 1: (1.3-2).
More preferably, the fumed silica is hydrophobic nano fumed silica and the calcium carbonate is heavy nano calcium carbonate.
The hydrophobic nano fumed silica is AEROSILR 8200.
The heavy nanometer calcium carbonate is IMERYS (Yirui stone) calcium carbonate S.
The applicant finds that when the fumed silica is used alone, the influence on the later strength of the coating adhesive is certain, and when the certain amount of the heavy nanometer calcium carbonate is added, the influence of the fumed silica on the later strength of the coating adhesive can be reduced.
Chain extender
The chain extender is an aromatic chain extender.
The aromatic chain extender is a condensation product of phthalic anhydride, butanediol and ethylene glycol.
Preferably, the weight average molecular weight of the aromatic chain extender is 400-1800; further preferably, the weight average molecular weight of the aromatic chain extender is 1000-1500; still more preferably, the aromatic chain extender has a weight average molecular weight of 1200.
The aromatic chain extender was purchased from Nanjing Spodol chemical Co.
The aromatic chain extender used in the invention can increase the adhesive force of the coating adhesive to the base material to a certain extent.
Isocyanates
The isocyanate is aromatic isocyanate.
The aromatic isocyanate is one or more of 4, 4 '-diphenylmethane diisocyanate and 2, 4' -diphenylmethane diisocyanate.
Preferably, the aromatic isocyanate is 4, 4' -diphenylmethane diisocyanate.
When 4, 4' -diphenylmethane diisocyanate is chosen, the adhesion of the coating paste is better, probably because of its better symmetry, thus increasing the initial strength of the system.
The 4, 4' -diphenylmethane diisocyanate is Wanhua MDI.
Catalyst and process for preparing same
In order to accelerate the curing rate of the coating adhesive, a catalyst is added into the system.
The catalyst is an organic amine catalyst.
Examples of the organic amine catalyst include DMDEE, DMAEE, tetramethylpropanediamine, tetramethyl-1, 6-hexanediamine, tetramethylhexanediamine and the like.
Preferably, the catalyst used is DMDEE.
The second aspect of the invention provides a preparation method of a universal coating adhesive, which comprises the following steps:
(1) adding polyether glycol, acrylic resin, a defoaming agent and a filler into a reaction kettle A with a high-speed dispersion characteristic, adjusting the temperature to 130-150 ℃, melting for 2 hours, and vacuumizing and dehydrating for 30 minutes;
(2) adding polyester polyol and polyurethane elastomer into a reaction kettle B, regulating the temperature to 130-150 ℃, melting for 1-1.5 hours, and vacuumizing and dehydrating for 30 minutes;
(3) adding a proper amount of the mixture in the reaction kettle A into the reaction kettle B, and then vacuumizing, stirring and dehydrating for 1 hour at the temperature of 120-140 ℃;
(4) cooling to 100-;
(5) cooling to 70 ℃, adding isocyanate, reacting and defoaming for 1-2 hours under the condition of introducing nitrogen, wherein the temperature of the whole reaction process is 80-120 ℃;
(6) after the reaction is finished, adding a catalyst, discharging under the protection of nitrogen, and sealing and packaging to obtain the universal coating adhesive.
Several specific examples of the present invention are given below, but the present invention is not limited by the examples.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Embodiment 1 of the present invention specifically provides a general-purpose coating adhesive, which comprises, by weight, 15 parts of polyether polyol, 10 parts of acrylic resin, 35 parts of polyester polyol, 0.01 part of a defoaming agent, 5 parts of a polyurethane elastomer, 1 part of a filler, 5 parts of a chain extender, 10 parts of isocyanate, and 0.03 part of a catalyst;
the polyether polyol is a mixture of polyether polyol with the functionality of 2 and the hydroxyl value of 56mg KOH/g and polyether polyol with the functionality of 4 and the hydroxyl value of 28mg KOH/g, wherein the weight ratio of the polyether polyol with the functionality of 2 and the hydroxyl value of 56mg KOH/g to the polyether polyol with the functionality of 4 and the hydroxyl value of 28mg KOH/g is 1: 2;
the acrylic resin is polar acrylic resin;
the hydroxyl content of the polar acrylic resin is 1.6%, and the acid value is 6mg KOH/g;
the polar acrylic resin is hydroxyl acrylic resin;
the polyester polyol comprises liquid polyester polyol, crystalline polyester polyol and amorphous polyester polyol, wherein the weight ratio of the polyester polyol to the crystalline polyester polyol to the amorphous polyester polyol is 2: 3: 1; the hydroxyl value of the liquid polyester polyol is 27-24 mg KOH/g; the glass transition temperature of the liquid polyester polyol is-20 ℃; the hydroxyl value of the crystalline polyester polyol is 27-34 mg KOH/g; the weight average molecular weight of the crystalline polyester polyol is 3500; the hydroxyl value of the amorphous polyester polyol is 31-39 mg KOH/g; the vitrification temperature of the amorphous polyester polyol is 30 ℃;
the polyester polyols also include high molecular weight polyester polyols; wherein the weight ratio of the high molecular weight polyester polyol to the crystalline polyester polyol is 1: 2; the weight average molecular weight of the high molecular weight polyester polyol is 20000, and the hydroxyl value of the high molecular weight polyester polyol is 4-6 mg KOH/g;
the polyurethane elastomer is a thermoplastic polyurethane elastomer;
the filler is a mixture of fumed silica and calcium carbonate, wherein the weight ratio of fumed silica to calcium carbonate is 1: 1.3; the fumed silica is hydrophobic nano fumed silica; the calcium carbonate is heavy nano calcium carbonate;
the chain extender is an aromatic chain extender;
the aromatic chain extender is a condensation product of phthalic anhydride, butanediol and glycol;
the weight average molecular weight of the aromatic chain extender is 1000;
the isocyanate is aromatic isocyanate; the aromatic isocyanate is 4, 4' -diphenylmethane diisocyanate;
the catalyst is DMDEE;
the preparation method of the universal coating adhesive comprises the following steps:
(1) adding polyether glycol, acrylic resin, a defoaming agent and a filler into a reaction kettle A with a high-speed dispersion characteristic, adjusting the temperature to 130 ℃, melting for 2 hours, and vacuumizing and dehydrating for 30 minutes;
(2) adding polyester polyol and polyurethane elastomer into a reaction kettle B, regulating the temperature to 130 ℃, melting for 1.5 hours, and vacuumizing and dehydrating for 30 minutes;
(3) adding a proper amount of the mixture in the reaction kettle A into the reaction kettle B, and then vacuumizing, stirring and dehydrating for 1 hour at the temperature of 120 ℃;
(4) cooling to 100 ℃, adding a chain extender into the reaction kettle B, and vacuumizing and dehydrating for 30 minutes;
(5) cooling to 70 ℃, adding isocyanate, reacting and defoaming for 2 hours in a nitrogen-filled state, wherein the temperature of the whole reaction process is 80 ℃;
(6) after the reaction is finished, adding a catalyst, discharging under the protection of nitrogen, and sealing and packaging to obtain the universal coating adhesive.
The polyether polyol is polyether 2020 with the functionality of 2 and the hydroxyl value of 56mg KOH/g, the polyether polyol with the functionality of 4 and the hydroxyl value of 28mg KOH/g is polyether 4040, and is purchased from Spilaulization chemical science and technology Co., Ltd; the hydroxyl acrylic resin is Setalux D A760 BA/X; the liquid polyester polyol is Yingchuang polyester polyol Dynacoll 7230; the crystalline polyester polyol is a winning polyester polyol Dynacoll 7380; the amorphous polyester polyol is Yingchuang polyester polyol Dynacoll 7130; the high molecular weight polyester polyol is purchased from hk-20000 of Jining HuaKai resin Co., Ltd; the defoaming agent is BYK-021; the thermoplastic polyurethane elastomer is Wanhua WHT-6232; the hydrophobic nano fumed silica is AEROSILR 8200; the heavy nanometer calcium carbonate is IMERYS (Yirui stone) calcium carbonate S; 4, 4' -diphenylmethane diisocyanate is Wanhua MDI; aromatic chain extenders are available from Nanjing Spodol chemical Co.
Example 2
Embodiment 2 of the present invention specifically provides a general-purpose coating adhesive, which comprises, by weight, 30 parts of polyether polyol, 20 parts of acrylic resin, 70 parts of polyester polyol, 0.05 part of a defoaming agent, 15 parts of a polyurethane elastomer, 5 parts of a filler, 10 parts of a chain extender, 20 parts of isocyanate, and 0.1 part of a catalyst;
the polyether polyol is a mixture of polyether polyol with the functionality of 2 and the hydroxyl value of 56mg KOH/g and polyether polyol with the functionality of 4 and the hydroxyl value of 28mg KOH/g, wherein the weight ratio of the polyether polyol with the functionality of 2 and the hydroxyl value of 56mg KOH/g to the polyether polyol with the functionality of 4 and the hydroxyl value of 28mg KOH/g is 1: 3;
the acrylic resin was the same as in example 1;
the polyester polyol comprises liquid polyester polyol, crystalline polyester polyol and amorphous polyester polyol, wherein the weight ratio of the polyester polyol to the crystalline polyester polyol to the amorphous polyester polyol is 4: 6: 3; the liquid polyester polyol, the crystalline polyester polyol and the amorphous polyester polyol are the same as those in example 1;
the polyester polyols also include high molecular weight polyester polyols; wherein the weight ratio of the high molecular weight polyester polyol to the crystalline polyester polyol is 1: 2; the high molecular weight polyester polyol is the same as in example 1;
the polyurethane elastomer was the same as in example 1;
the filler is a mixture of fumed silica and calcium carbonate, wherein the weight ratio of fumed silica to calcium carbonate is 1: 2; the fumed silica is hydrophobic nano fumed silica; the calcium carbonate is heavy nano calcium carbonate;
the chain extender is the same as in example 1;
the isocyanate was the same as in example 1;
the catalyst was the same as in example 1;
the preparation method of the universal coating adhesive comprises the following steps:
(1) adding polyether glycol, acrylic resin, a defoaming agent and a filler into a reaction kettle A with a high-speed dispersion characteristic, adjusting the temperature to 150 ℃, melting for 2 hours, and vacuumizing and dehydrating for 30 minutes;
(2) adding polyester polyol and polyurethane elastomer into a reaction kettle B, adjusting the temperature to 150 ℃, melting for 1.5 hours, and vacuumizing and dehydrating for 30 minutes;
(3) adding a proper amount of the mixture in the reaction kettle A into the reaction kettle B, and then vacuumizing, stirring and dehydrating for 1 hour at the temperature of 140 ℃;
(4) cooling to 110 ℃, adding a chain extender into the reaction kettle B, and vacuumizing and dehydrating for 30 minutes;
(5) cooling to 70 ℃, adding isocyanate, reacting and defoaming for 1 hour under the state of introducing nitrogen, wherein the temperature of the whole reaction process is 120 ℃;
(6) after the reaction is finished, adding a catalyst, discharging under the protection of nitrogen, and sealing and packaging to obtain the universal coating adhesive.
The polyether polyol is polyether 2020 with the functionality of 2 and the hydroxyl value of 56mg KOH/g, the polyether polyol with the functionality of 4 and the hydroxyl value of 28mg KOH/g is polyether 4040, and is purchased from Spilaulization chemical science and technology Co., Ltd; the defoaming agent is BYK-021; the hydrophobic nano fumed silica is AEROSILR 8200; the heavy nanometer calcium carbonate is IMERYS (Yirui stone) calcium carbonate S.
Example 3
Embodiment 3 of the present invention specifically provides a general-purpose coating adhesive, which comprises, by weight, 26 parts of polyether polyol, 15 parts of acrylic resin, 59 parts of polyester polyol, 0.03 part of a defoaming agent, 9 parts of a polyurethane elastomer, 2.8 parts of a filler, 7.2 parts of a chain extender, 15 parts of isocyanate, and 0.06 part of a catalyst;
the polyether polyol is a mixture of polyether polyol with the functionality of 2 and the hydroxyl value of 56mg KOH/g and polyether polyol with the functionality of 4 and the hydroxyl value of 28mg KOH/g, wherein the weight ratio of the polyether polyol with the functionality of 2 and the hydroxyl value of 56mg KOH/g to the polyether polyol with the functionality of 4 and the hydroxyl value of 28mg KOH/g is 1: 2.5;
the acrylic resin was the same as in example 1;
the polyester polyol comprises liquid polyester polyol, crystalline polyester polyol and amorphous polyester polyol, wherein the weight ratio of the polyester polyol to the crystalline polyester polyol to the amorphous polyester polyol is 3: 5: 2; the liquid polyester polyol, the crystalline polyester polyol and the amorphous polyester polyol are the same as those in example 1;
the polyester polyols also include high molecular weight polyester polyols; wherein the weight ratio of the high molecular weight polyester polyol to the crystalline polyester polyol is 1: 2; the high molecular weight polyester polyol is the same as in example 1;
the polyurethane elastomer was the same as in example 1;
the filler is a mixture of fumed silica and calcium carbonate, wherein the weight ratio of fumed silica to calcium carbonate is 1: 1.6; the fumed silica is hydrophobic nano fumed silica; the calcium carbonate is heavy nano calcium carbonate;
the chain extender is the same as in example 1;
the isocyanate was the same as in example 1;
the catalyst was the same as in example 1;
the preparation method of the universal coating adhesive comprises the following steps:
(1) adding polyether glycol, acrylic resin, a defoaming agent and a filler into a reaction kettle A with a high-speed dispersion characteristic, adjusting the temperature to 140 ℃, melting for 2 hours, and vacuumizing and dehydrating for 30 minutes;
(2) adding polyester polyol and polyurethane elastomer into a reaction kettle B, adjusting the temperature to 140 ℃, melting for 1.2 hours, and vacuumizing and dehydrating for 30 minutes;
(3) adding a proper amount of the mixture in the reaction kettle A into the reaction kettle B, and then vacuumizing, stirring and dehydrating for 1 hour at the temperature of 130 ℃;
(4) cooling to 105 ℃, adding a chain extender into the reaction kettle B, and vacuumizing and dehydrating for 30 minutes;
(5) cooling to 70 ℃, adding isocyanate, reacting and defoaming for 1.5 hours in a nitrogen-filled state, wherein the temperature of the whole reaction process is 100 ℃;
(6) after the reaction is finished, adding a catalyst, discharging under the protection of nitrogen, and sealing and packaging to obtain the universal coating adhesive.
The polyether polyol is polyether 2020 with the functionality of 2 and the hydroxyl value of 56mg KOH/g, the polyether polyol with the functionality of 4 and the hydroxyl value of 28mg KOH/g is polyether 4040, and is purchased from Spilaulization chemical science and technology Co., Ltd; the defoaming agent is BYK-021; the hydrophobic nano fumed silica is AEROSILR 8200; the heavy nanometer calcium carbonate is IMERYS (Yirui stone) calcium carbonate S.
Example 4
Example 4 of the present invention specifically provides a general-purpose type of coating adhesive, which is similar to example 3, except that no crystalline polyester polyol is present.
Example 5
Example 5 of the present invention specifically provides a general-purpose type coating adhesive, which is different from example 3 in that no liquid polyester polyol is present.
Example 6
Example 6 of the present invention specifically provides a general-purpose type coating adhesive, which is different from example 3 in that calcium carbonate is not present.
Example 7
Example 7 of the present invention specifically provides a general-purpose type coating adhesive, which is the same as example 3, except that the aromatic isocyanate is MDI-50, which is purchased in wanhua.
Performance testing
1. The peel strength of the coating adhesive in examples 1-3 at 180 degrees is determined according to the standard GT/T2990-1995, wherein the coating base material is a wood-plastic wallboard-PVC film, and the peel strength is greater than 45N/25mm, which indicates that the coating adhesive has good peel strength;
2. the viscosity of the coating glue in the examples 1-3 is measured according to a method commonly used in the field, and then the viscosity is tested after the coating glue is continuously heated for 48 hours at 110 ℃, wherein the change of the viscosity is not more than 2 times, which indicates that the coating glue completely meets the use requirements of glue melting equipment of a pressure plate and a glue cylinder.
3. Taking 10 groups of samples of the coating glue coated density board-CPL film in the embodiment, wherein the gluing temperature is 120 ℃, the glue amount is 50 g/m, and observing the conditions of the glued samples by experienced experimenters in the field;
scoring the curling phenomenon of the CPL film, wherein the full score is 100, averaging and averaging are carried out, the lower the score is, the more serious the curling phenomenon is, namely the lower the initial strength is, the 100-time-sharing curling phenomenon does not occur, averaging and averaging are carried out, the score is more than or equal to 95, the initial strength is 1 grade, and the score is more than or equal to 85 and less than 95, the initial strength is 2 grade; the initial strength of the fraction is 3 grades when the fraction is more than or equal to 70 minutes and less than 85 minutes; the fraction is less than 70 and is divided into 4 grades of initial strength;
after curing for 48 hours, tearing the CPL film, scoring the damage degree of the film, wherein the full score is 100, averaging and equally dividing, the higher the score is, the larger the damage degree of the film is, namely the larger the later strength of the coating adhesive is, the later strength is grade 1, and the later strength is grade 2 when the score is more than or equal to 85 and less than 95; the later strength of the score is 3 grades when the score is greater than or equal to 70 scores and less than 85 scores; the score is less than 70 and is classified as late strength 4;
the test results are shown in table 1:
TABLE 1
As can be seen from the test results in Table 1, the coating compound provided by the invention has good initial strength and late strength.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The universal coating adhesive is characterized by comprising, by weight, 15-30 parts of polyether polyol, 10-20 parts of acrylic resin, 35-80 parts of polyester polyol, 0.01-0.05 part of a defoaming agent, 5-15 parts of a polyurethane elastomer, 0-5 parts of a filler, 5-10 parts of a chain extender, 10-20 parts of isocyanate and 0.01-0.1 part of a catalyst.
2. The universal coating according to claim 1, wherein the polyether polyol has a functionality of 2 to 6 and a hydroxyl value of 19 to 56 mgKOH/g.
3. The universal coating adhesive according to claim 1, wherein the acrylic resin is a polar acrylic resin.
4. The universal coating according to claim 1, wherein said polyester polyol comprises liquid polyester polyol, crystalline polyester polyol, amorphous polyester polyol.
5. The universal coating according to claim 4, wherein said polyester polyol further comprises a high molecular weight polyester polyol; wherein the weight ratio of the high molecular weight polyester polyol to the crystalline polyester polyol is 1: 2.
6. the coating compound of claim 1, wherein the filler is at least one of talc, fumed silica, and calcium carbonate.
7. The universal coating adhesive according to claim 1, wherein the chain extender is an aromatic chain extender.
8. The universal coating according to claim 1, wherein said isocyanate is an aromatic isocyanate.
9. The universal coating adhesive according to claim 1, wherein the catalyst is an organic amine catalyst.
10. A method for preparing a universal coating glue according to any one of claims 1 to 9, characterized in that it comprises the following steps:
(1) adding polyether glycol, acrylic resin, a defoaming agent and a filler into a reaction kettle A with a high-speed dispersion characteristic, adjusting the temperature to 130-150 ℃, melting for 2 hours, and vacuumizing and dehydrating for 30 minutes;
(2) adding polyester polyol and polyurethane elastomer into a reaction kettle B, regulating the temperature to 130-150 ℃, melting for 1-1.5 hours, and vacuumizing and dehydrating for 30 minutes;
(3) adding a proper amount of the mixture in the reaction kettle A into the reaction kettle B, and then vacuumizing, stirring and dehydrating for 1 hour at the temperature of 120-140 ℃;
(4) cooling to 100-;
(5) cooling to 70 ℃, adding isocyanate, reacting and defoaming for 1-2 hours under the condition of introducing nitrogen, wherein the temperature of the whole reaction process is 80-120 ℃;
(6) after the reaction is finished, adding a catalyst, discharging under the protection of nitrogen, and sealing and packaging to obtain the universal coating adhesive.
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