CN114605954A - High-adhesion and water-boiling fast-degumming two-component polyurethane adhesive, preparation method and application thereof - Google Patents
High-adhesion and water-boiling fast-degumming two-component polyurethane adhesive, preparation method and application thereof Download PDFInfo
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- CN114605954A CN114605954A CN202210182872.9A CN202210182872A CN114605954A CN 114605954 A CN114605954 A CN 114605954A CN 202210182872 A CN202210182872 A CN 202210182872A CN 114605954 A CN114605954 A CN 114605954A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 74
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 74
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 238000009835 boiling Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 47
- 229920000570 polyether Polymers 0.000 claims abstract description 47
- 229920005862 polyol Polymers 0.000 claims abstract description 36
- 150000003077 polyols Chemical class 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000004088 foaming agent Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 16
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 239000000049 pigment Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 15
- 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 claims description 14
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 8
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000005187 foaming Methods 0.000 claims description 3
- 241000208140 Acer Species 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 17
- 239000004033 plastic Substances 0.000 abstract description 17
- 239000004593 Epoxy Substances 0.000 abstract description 12
- 239000012790 adhesive layer Substances 0.000 abstract description 9
- 239000002313 adhesive film Substances 0.000 abstract description 4
- 229920006332 epoxy adhesive Polymers 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 235000006550 Liquidambar Nutrition 0.000 description 1
- 241000208682 Liquidambar Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 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 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-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
-
- 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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
-
- 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
- C08G18/65—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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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 discloses a high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2-2.5: 1; the component A comprises the following raw materials: polyether polyol, polyester polyol, a cross-linking agent, an accelerator, a diluent, a water removing agent, a filler, an anti-settling agent, a foaming agent and a pigment filler; the component B comprises the following raw materials: the polyurethane adhesive is prepared by the steps of respectively preparing a component A and a component B, mixing and the like. Compared with an epoxy system adhesive, the polyurethane adhesive disclosed by the invention is easier to degum at 90-100 ℃ after being boiled in water, the adhesive layer is adhered to a plastic plate, the adhesive film is simple to process, the epoxy system adhesive needs longer time for degum, and the adhesive layer can be adhered to a workpiece plate and is difficult to remove.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive, and a preparation method and application thereof.
Background
With the development of society and the rapid increase of energy demand, the photovoltaic industry also rapidly increases. The cutting of the silicon wafer is an indispensable link in the photovoltaic industry, auxiliary materials used in the cutting of the silicon wafer also occupy an important position, and the adhesive plays an irreplaceable role in the cutting. The present conventionally used adhesive is mainly an epoxy adhesive, and the epoxy adhesive used for adhering a bottom plate in silicon wafer cutting has certain defects, and mainly has poor adhesion to a nonpolar substrate such as a plastic plate, so that the bottom plate is difficult to remove in the process of boiling off the bottom plate by post-treatment water, and after the substrate is removed, an adhesive layer adheres to the base and needs to be removed manually, so that the treatment is difficult, time and labor are wasted, and the epoxy adhesive belongs to dangerous chemicals and needs more treatment cost. Aiming at the defect that the epoxy adhesive is adhered to the bottom plate, the experiment designs the two-component polyurethane adhesive which has higher adhesive force, can be rapidly degummed by boiling water and has simple post-treatment and environmental protection for the non-polar plastic plate.
Disclosure of Invention
The invention provides a high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive, a preparation method and application thereof, and aims to solve the problems that the existing epoxy adhesive base plate adhesive is low in adhesion to a non-polar plastic plate, water-boiling degumming is difficult, and post-treatment is time-consuming, labor-consuming and high in cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2-2.5: 1; the component A comprises the following raw materials in parts by mass: 25-35 parts of polyether polyol, 10-15 parts of polyester polyol, 2-6 parts of a cross-linking agent, 1-1.5 parts of an accelerator, 8-25 parts of a diluent, 1-3 parts of a water removing agent, 30-44.5 parts of a filler, 0.3-1 part of an anti-settling agent, 1-5 parts of a foaming agent and 1-3 parts of a pigment and filler; the component B comprises the following raw materials: the adhesive comprises diphenylmethane diisocyanate and polyether polyol, wherein the mass ratio of the diphenylmethane diisocyanate to the polyether polyol is 6-7: 3-4.
In a preferred technical scheme, the polyether polyol comprises one or more of 3-functional polyether 6000, 3-functional polyether 3000, 2-functional polyether 2000 and polyether polyol with molecular weight of 300, 600 and 800. Experiments show that 2-functional polyether 2000 is adopted as a modifier through screening optimization, so that the modified isocyanate curing agent has a flexible chain segment, the toughness of the final polyurethane adhesive is improved, and the polyurethane adhesive has higher toughness compared with an epoxy system adhesive.
In a preferred technical scheme, the polyester polyol comprises one or more of molecular weights of 3000, 5000, 6000 and 8000.
In a preferred technical scheme, the cross-linking agent comprises one or two of trimethylolpropane and dipropylene glycol. Because polyether polyol and diphenylmethane diisocyanate react slowly, the addition of the cross-linking agent can improve the operation time, and particularly when trimethylolpropane and dipropylene glycol are used in combination, the effect is better.
In a preferred technical scheme, the accelerator comprises one or more of dibutyltin dilaurate, tertiary amine DMP-30 and isooctanoic acid. Because the polyether polyol and the diphenylmethane diisocyanate have slower reaction, the operation time is obviously improved and the production period is shortened by adding the accelerator on the basis of adding the cross-linking agent, and the effect is better when the tertiary amine DMP-30 and the isooctanoic acid are used in a matching way.
In a preferred technical scheme, the diluent comprises one or two of dibutyl phthalate and maple syrup.
In the preferred technical scheme, the water removal agent is a 3A molecular sieve, and the performance can be prevented from being influenced by the reaction of isocyanate and water in the air by adding the water removal agent.
In a preferred technical scheme, the foaming agent is a loose microsphere foaming agent, and the foaming temperature is 70-100 ℃. Experiments show that compared with epoxy system adhesives, the polyurethane adhesive degumming agent prepared by boiling in water is easier to degum at 90-100 ℃, and the adhesive layer is adhered to a plastic plate, so that the adhesive film is simple to treat, and the treatment cost is lower.
The invention also provides a preparation method of the high-adhesion and water-boiling quick-degumming two-component polyurethane adhesive, which comprises the following steps:
(1) taking parts by mass as a unit, sequentially adding 25-35 parts of polyether polyol, 10-15 parts of polyester polyol, 2-6 parts of a cross-linking agent and 8-25 parts of a diluent, then vacuumizing to remove water, then cooling and stirring while adding 1-1.5 parts of an accelerator, 1-3 parts of a water removing agent, 30-44.5 parts of a filler, 0.3-1 part of an anti-settling agent, 1-5 parts of a foaming agent and 1-3 parts of a pigment and filler, and stirring to obtain a component A;
(2) sequentially adding 60-70 parts of diphenylmethane diisocyanate and 30-40 parts of polyether polyol into a reaction kettle by taking parts by mass as a unit, and vacuumizing and stirring under a closed condition to prepare a component B of the modified isocyanate curing agent;
(3) and mixing the component A and the component B according to the mass ratio of 2-2.5:1 to prepare the high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive.
The invention also provides application of the high-adhesion and water-boiling quick-degumming two-component polyurethane adhesive to adhering a bottom plate (plastic plate) in silicon wafer cutting.
The technical principle of the invention is as follows:
according to the invention, polyether polyol and isocyanate are used for reaction, soft and hard chain segment crosslinking is generated in the reaction, a polyurethane bond generated by the reaction has special adhesive force to the surface of a plastic plate, and an auxiliary accelerator and a crosslinking agent are needed to improve the operation time due to the slow reaction, so that the production period is shortened; isocyanate is easy to react with water, and the performance of the isocyanate is prevented from being influenced by the reaction of the isocyanate and the water in the air by adding the water removing agent; the foaming agent mainly has the effect of reducing the temperature resistance after curing so as to improve the boiling degumming effect, compared with an epoxy system adhesive, the polyurethane adhesive disclosed by the invention is easier to degum at 90-100 ℃ in boiling degumming, the adhesive layer is adhered to a plastic plate, the adhesive film is simple to treat, the existing epoxy system adhesive needs longer time for degumming, the adhesive layer can be adhered to a workpiece plate and is difficult to remove, time and labor are wasted, and the treatment cost is higher.
Compared with the prior art, the invention has the advantages that:
1. the adhesive system of the present invention is a polyurethane system, which has a higher adhesion than an epoxy system, and especially a better adhesion to non-polar plastic plates, since the isocyanate bonds in the polyurethane adhesive have a better adhesion to the plastic plates than the epoxy and hydroxyl groups in the epoxy adhesive.
2. The polyurethane is a self-made modified isocyanate curing agent, and 2-functional polyether 2000 is adopted as a modifier through screening optimization, so that the modified isocyanate curing agent has a flexible chain segment, the toughness of the final polyurethane adhesive is improved, and the polyurethane adhesive has higher toughness compared with an epoxy system adhesive.
3. The polyether polyol adopted by the invention is matched with a hydroxyl system of the polyester polyol, and the flexible connection is combined with the hard chain segment, so that the polyurethane adhesive disclosed by the invention has toughness and also keeps high bonding performance.
4. Compared with an epoxy system adhesive, the polyurethane adhesive disclosed by the invention is easier to degum at 90-100 ℃ after being boiled in water, the adhesive layer is adhered to a plastic plate, the adhesive film is simple to process, the epoxy system adhesive needs longer time for degum, the adhesive layer can be adhered to a workpiece plate and is difficult to remove, and time and labor are wasted.
5. The polyurethane adhesive disclosed by the invention belongs to an environment-friendly adhesive, does not belong to hazardous chemicals, is simple in post-treatment and needs lower treatment cost.
Detailed Description
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
A high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2-2.5: 1; the component A comprises the following raw materials in parts by mass: 25-35 parts of polyether polyol, 10-15 parts of polyester polyol, 2-6 parts of a cross-linking agent, 1-1.5 parts of an accelerator, 8-25 parts of a diluent, 1-3 parts of a water removing agent, 30-44.5 parts of a filler, 0.3-1 part of an anti-settling agent, 1-5 parts of a foaming agent and 1-3 parts of a pigment and filler; the component B comprises the following raw materials: the adhesive comprises diphenylmethane diisocyanate and polyether polyol, wherein the mass ratio of the diphenylmethane diisocyanate to the polyether polyol is 6-7: 3-4.
The polyether polyol comprises one or more of 3-functional polyether 6000, 3-functional polyether 3000, 2-functional polyether 2000 and polyether polyol with molecular weight of 300, 600 and 800.
The polyester polyol comprises one or more of molecular weight 3000, 5000, 6000 and 8000.
The cross-linking agent comprises one or two of trimethylolpropane and dipropylene glycol.
The accelerator comprises one or more of dibutyltin dilaurate, tertiary amine DMP-30 and isooctanoic acid.
The diluent comprises one or two of dibutyl phthalate and liquidambar cathayensis.
The water removing agent is a 3A molecular sieve.
The filler comprises one or more of calcium carbonate, talcum powder and silica powder.
The anti-settling agent comprises fumed silica.
The foaming agent is a loose-leaf microsphere foaming agent, and the foaming temperature is 70-100 ℃.
The pigment and filler is titanium dioxide.
The preparation method of the high-adhesion and water-boiling quick-degumming two-component polyurethane adhesive comprises the following steps:
(1) taking parts by mass as a unit, sequentially adding 25-35 parts of polyether polyol, 10-15 parts of polyester polyol, 2-6 parts of cross-linking agent and 8-25 parts of diluent, vacuumizing at 90 ℃ to remove water for 2 hours, then cooling to 50 ℃, adding 1-1.5 parts of accelerant, 1-3 parts of water removing agent, 30-44.5 parts of filler, 0.3-1 part of anti-settling agent, 1-5 parts of foaming agent and 1-3 parts of pigment and filler while stirring, and stirring for 2 hours to obtain a component A;
(2) sequentially adding 60-70 parts of crude diphenylmethane diisocyanate MDI and 30-40 parts of polyether polyol into a reaction kettle by taking parts by mass as a unit, and vacuumizing and stirring for 3 hours under a closed condition to prepare a component B of the modified isocyanate curing agent;
(3) and mixing the component A and the component B according to the mass ratio of 2-2.5:1 to prepare the high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive.
The following is a more specific example.
Example 1
A high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2: 1; the component A is prepared from 25g of 3-functional molecular weight 6000 polyether polyol, 10g of 3-functional molecular weight 5000 polyester polyol, 4g of trimethylolpropane, 8g of dibutyl phthalate, 0.5g of tertiary amine DMP-30, 0.5g of isooctanoic acid, 3g of 3A molecular sieve, 3g of rosin microsphere foaming agent, 0.5g of fumed silica, 1g of titanium dioxide and 44.5g of calcium carbonate; the B component was prepared from 60g of crude MID, 40g of a 2-functional 3000 molecular weight polyether polyol.
The preparation method of the two-component polyurethane adhesive comprises the following steps:
step 1, adding 25g of 3-functional molecular weight 6000 polyether polyol, 10g of 3-functional molecular weight 5000 polyester polyol, 4g of trimethylolpropane and 8g of dibutyl phthalate in sequence, vacuumizing at 90 ℃ to remove water for 2 hours, cooling to 50 ℃, adding 0.5g of tertiary amine DMP-30, 0.5g of isooctanoic acid, 3g of 3A molecular sieve, 3g of pine microsphere foaming agent, 0.5g of fumed silica, 1g of titanium dioxide and 44.5g of calcium carbonate in sequence while stirring, and stirring for 2 hours to obtain a component A;
step 2: sequentially adding 60g of crude MDI and 40g of polyether polyol with the molecular weight of 2 functional groups of 3000 into a reaction kettle, and stirring for 3 hours under the condition of sealing while vacuumizing to prepare a component B of the modified isocyanate curing agent;
(3) and mixing the component A and the component B according to the mass ratio of 2:1 to prepare the high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive.
Example 2
A high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 2.5: 1; the component A is prepared from 25g of 3-functional molecular weight 6000 polyether polyol, 10g of 2-functional molecular weight 3000 polyether polyol, 10g of 3-functional molecular weight 5000 polyester polyol, 2g of trimethylolpropane, 2g of dipropylene glycol, 8g of dibutyl phthalate, 1g of tertiary amine DMP-30, 0.5g of isooctanoic acid, 3g of 3A molecular sieve, 3g of a loose microsphere foaming agent, 0.5g of fumed silica, 1g of titanium dioxide and 34g of calcium carbonate; the B component was prepared from 70g of crude MID, 30g of a 2-functional 3000 molecular weight polyether polyol.
The preparation method of the two-component polyurethane adhesive comprises the following steps:
step 1, adding 25g of 6000 polyether polyol with 3 functional molecular weight, 10g of 3000 polyether polyol with 2 functional molecular weight, 10g of 5000 polyester polyol with 3 functional molecular weight, 2g of trimethylolpropane, 2g of dipropylene glycol and 8g of dibutyl phthalate in sequence, vacuumizing at 90 ℃ to remove water for 2h, cooling to 50 ℃, adding 1g of tertiary amine DMP-30, 0.5g of isooctanoic acid, 3g of 3A molecular sieve, 3g of a loose microsphere foaming agent, 0.5g of fumed silica, 1g of titanium dioxide and 34g of calcium carbonate in sequence while stirring to prepare a component A, and stirring for 2 h;
and 2, step: adding 70g of crude MDI and 30g of 2-functional group molecular weight 3000 polyether polyol into a reaction kettle in sequence, and stirring for 3 hours under the condition of sealing while vacuumizing to prepare a component B of the modified isocyanate curing agent;
(3) and mixing the component A and the component B according to the mass ratio of 2.5:1 to prepare the high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive.
Comparative example 1
The adhesives are prepared by adopting the methods of examples 1 to 4 in Chinese patent document 'a water boiling type modified epoxy adhesive for cutting a silicon single crystal rod and a preparation method thereof (patent number: ZL 201210563781.6').
The adhesives prepared in examples 1-2 and comparative example 1 were cured at 25 ℃ for 3 hours, and the performance was tested, with the results shown in table 1.
TABLE 1 Property parameters after 3h of curing
Note: the T-type drawing strength is detected by adopting a standard GB/T7291; the elongation at break is detected by adopting standard GB/T6329; the peel strength of the plastic plate is detected by adopting standard GB/T7122; degumming time: water bath is carried out in a water bath kettle at the temperature of 90-100 ℃, and the plastic plate is separated from the workpiece plate; distribution of the degumming glue layer: and (3) residual glue film distribution after the plastic plate is separated from the workpiece plate.
As can be seen from Table 1, the elongation at break of the polyurethane adhesive is much higher than that of the epoxy adhesive in the comparative example 1, at least 30.7% higher, and the T-shaped pull strength is superior to that of the epoxy adhesive in the comparative example 1, at least 42.9% higher, because the epoxy adhesive is higher in brittleness and poorer in toughness; compared with the peel strength of plastics, the level of the polyurethane adhesive is equivalent to that of the prior art (comparative example 1), and the polyurethane adhesive has good peel strength; according to the degumming effect and the distribution condition of the adhesive layers, the polyurethane adhesive is degummed better than the epoxy adhesive under the condition of water boiling, the degumming time is shorter, the degumming time is at least shortened by more than 66.7%, and the post-treatment is simpler (the polyurethane adhesive is attached to a plastic plate and is easy to remove, while the polyurethane adhesive in the comparative example 1 is attached to the plastic plate and is difficult to remove), so that the polyurethane system adhesive has remarkable progress compared with the epoxy system adhesive in the prior art. In conclusion, the polyurethane adhesive has better application prospect in the field of photovoltaic cutting than an epoxy adhesive.
The foregoing shows and describes the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the preferred embodiments of the present invention are described in the above embodiments and the description only, and that the present invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit and scope of the present invention, which fall within the scope of the claimed invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A high-adhesion double-component polyurethane adhesive capable of rapidly degumming by water boiling is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 2-2.5: 1; the component A comprises the following raw materials in parts by mass: 25-35 parts of polyether polyol, 10-15 parts of polyester polyol, 2-6 parts of a cross-linking agent, 1-1.5 parts of an accelerator, 8-25 parts of a diluent, 1-3 parts of a water removing agent, 30-44.5 parts of a filler, 0.3-1 part of an anti-settling agent, 1-5 parts of a foaming agent and 1-3 parts of a pigment and filler; the component B comprises the following raw materials: the adhesive comprises diphenylmethane diisocyanate and polyether polyol, wherein the mass ratio of the diphenylmethane diisocyanate to the polyether polyol is 6-7: 3-4.
2. The high adhesion, water-boiled quick-debonding two-component polyurethane adhesive according to claim 1, wherein the polyether polyol comprises one or more of 6000 functional polyether, 3000 functional polyether, 2000 functional polyether, and polyether polyol with molecular weight of 300, 600, 800.
3. The high adhesion, water-boil rapid debonding two-component polyurethane adhesive of claim 1, wherein the polyester polyol comprises one or more of molecular weights 3000, 5000, 6000, 8000.
4. The high adhesion, water-boiled quick-debonding two-component polyurethane adhesive according to claim 1, wherein the crosslinking agent comprises one or both of trimethylolpropane and dipropylene glycol.
5. The high adhesion, quick water boil off two-component polyurethane adhesive of claim 1 wherein the accelerator comprises one or more of dibutyl tin dilaurate, tertiary amine DMP-30, isooctanoic acid.
6. The high adhesion, water boiling fast degumming two-component polyurethane adhesive according to claim 1, wherein the diluent comprises one or both of dibutyl phthalate and maple.
7. The high-adhesion water-boiling rapid-degumming two-component polyurethane adhesive according to claim 1, wherein the water scavenger is a 3A molecular sieve.
8. The high adhesion, water-boiling fast degumming two-component polyurethane adhesive according to claim 1, wherein the foaming agent is a loose-leaf microsphere foaming agent, and the foaming temperature is 70-100 ℃.
9. A method of preparing a high adhesion, water boiling fast debonding two component polyurethane adhesive according to any one of claims 1-8, comprising the steps of:
(1) taking parts by mass as a unit, sequentially adding 25-35 parts of polyether polyol, 10-15 parts of polyester polyol, 2-6 parts of a cross-linking agent and 8-25 parts of a diluent, then vacuumizing to remove water, then cooling and stirring while adding 1-1.5 parts of an accelerator, 1-3 parts of a water removing agent, 30-44.5 parts of a filler, 0.3-1 part of an anti-settling agent, 1-5 parts of a foaming agent and 1-3 parts of a pigment and filler, and stirring to obtain a component A;
(2) sequentially adding 60-70 parts of diphenylmethane diisocyanate and 30-40 parts of polyether polyol into a reaction kettle by taking parts by mass as a unit, and vacuumizing and stirring under a closed condition to prepare a component B of the modified isocyanate curing agent;
(3) and mixing the component A and the component B according to the mass ratio of 2-2.5:1 to prepare the high-adhesion and water-boiling fast-degumming two-component polyurethane adhesive.
10. The use of the high adhesion, water-boiled rapid-debonding two-component polyurethane adhesive prepared according to the method of claim 9, wherein the adhesive is used for bonding a base plate in silicon wafer cutting.
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