CN114316178B - Polyurethane resin for thermal transfer printing, preparation method thereof, working slurry and thermal transfer printing film - Google Patents
Polyurethane resin for thermal transfer printing, preparation method thereof, working slurry and thermal transfer printing film Download PDFInfo
- Publication number
- CN114316178B CN114316178B CN202111530467.3A CN202111530467A CN114316178B CN 114316178 B CN114316178 B CN 114316178B CN 202111530467 A CN202111530467 A CN 202111530467A CN 114316178 B CN114316178 B CN 114316178B
- Authority
- CN
- China
- Prior art keywords
- thermal transfer
- polyurethane resin
- parts
- polyester diol
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 101
- 238000010023 transfer printing Methods 0.000 title claims abstract description 66
- 239000002002 slurry Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 150000002009 diols Chemical class 0.000 claims abstract description 49
- 229920000728 polyester Polymers 0.000 claims abstract description 49
- 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 abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 86
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 229920005586 poly(adipic acid) Polymers 0.000 claims description 12
- 239000013638 trimer Substances 0.000 claims description 11
- -1 aliphatic isocyanate Chemical class 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical group O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000010020 roller printing Methods 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Substances OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 abstract description 23
- 238000001816 cooling Methods 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 description 38
- 238000007731 hot pressing Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 24
- 101000573147 Arabidopsis thaliana Pectinesterase 6 Proteins 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000010985 leather Substances 0.000 description 12
- 229920000742 Cotton Polymers 0.000 description 11
- 229920002635 polyurethane Polymers 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 238000010030 laminating Methods 0.000 description 9
- 238000007639 printing Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000006188 syrup Substances 0.000 description 5
- 235000020357 syrup Nutrition 0.000 description 5
- 238000009965 tatting Methods 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Abstract
The invention belongs to the technical field of polyurethane resin, and particularly relates to polyurethane resin for thermal transfer printing, a preparation method thereof, working slurry and a thermal transfer film. The polyurethane resin for thermal transfer printing is prepared from the following raw materials: a polyadipic polyester diol, a polyphthalic polyester diol, diphenylmethane-4, 4' -diisocyanate and a solvent. The polyurethane resin for thermal transfer printing has good thermal bonding performance under the state of heating film formation, and realizes good adhesion with base cloth; after cooling, the film can be quickly crystallized and formed, and after being peeled off and separated from the OPP film, the surface is ensured to be smooth and heat-resistant.
Description
Technical Field
The invention belongs to the technical field of polyurethane resin, and particularly relates to polyurethane resin for thermal transfer printing, a preparation method thereof, working slurry and a thermal transfer film.
Background
The technical cloth is a novel sofa fabric and is praised as a breathing fabric. As the fabric has the texture and the color of leather and has excellent air permeability of the fabric sofa, the fabric is popular with environment-friendly operators and animal protectors once being pushed out, and scientific and technological fabric sofas are popular with domestic and foreign consumer groups.
In the synthetic leather industry, an OPP film is used as a transfer substrate, polyurethane resin is coated on the OPP film, and finally the polyurethane resin is transferred onto a base cloth (generally woven suede or imitation cotton velvet) in a thermal transfer mode to form a technical cloth sofa fabric.
The conventional thermal transfer process is as follows:
OPP film roller, coating polyurethane on the printing surface of the screen roller, forming a film and drying in an oven 1, hot pressing by a hot pressing roller, laminating with woven suede or imitation cotton velvet, drying in an oven 2, cooling, and rolling after peeling off the OPP film.
The process flow of traditional heat transfer printing can be seen that in the whole production process, two times of oven drying are used, the first time of drying is to dry the solvent in the polyurethane working slurry to form a film, then the film is heated and attached through a hot press roller, the second time of oven drying is to dry the residual solvent, and after the residual solvent is cooled through a cooling roller, the film is peeled and wound from the OPP film.
In order to further improve the production efficiency, current synthetic leather practitioners try to use a new thermal transfer process, which is as follows:
OPP film roller, coating polyurethane on the printing surface of the screen roller, forming a film and drying in an oven 1, hot pressing by a hot pressing roller, laminating with woven suede or imitation cotton velvet, cooling, and rolling after peeling off the OPP film.
Compared with the traditional process, in the new thermal transfer printing process, after the hot pressing roller is used for hot pressing and laminating with the woven suede or the imitation cotton velvet (abbreviated as technical cloth), the second drying of the oven is not needed, the rolling is directly cooled, the number of one-time oven drying is reduced, the energy is saved, and meanwhile, the production efficiency is improved.
For the conventional thermal transfer process, the performance requirements for the polyurethane resin used for surface coating are: as long as the requirements of good adhesion with the base cloth in the thermal transfer printing process after film formation are met, after the film is dried for the second time, the surface of the film is peeled off from the OPP film, the heat-resistant adhesive is good, the smoothness is good, and the resin can meet the requirements of the traditional thermal transfer printing process on polyurethane resin.
For the new thermal transfer process, the polyurethane resin for surface coating is required to be used due to the lack of a second drying process, and the polyurethane resin can be dried quickly after the hot pressing and laminating of the hot pressing roller, so that the polyurethane resin is required to have the following characteristics besides the advantages of good adhesiveness, good heat-resistant viscosity and good smoothness of the polyurethane resin used in the traditional thermal transfer process: 1. can be dried quickly in a short time and form a film quickly; the prior art comprises an OPP film roller, coating polyurethane on the printing surface of a screen roller, forming a film and drying by a baking oven 1, hot-pressing and laminating the film with tatting suede or imitation cotton velvet by a hot-pressing roller, drying and cooling by the baking oven 2, and rolling the product after being peeled from the OPP film. In the technology, the drying temperature of the oven 1 is 65-75 ℃, and the heating and drying time of the oven 1 is 40-60s; the drying temperature of the oven 2 is 65-75 ℃, and the heating and drying time of the oven 2 is 20-30s. And after the product is dried by a two-stage oven and cooled (cooling roller cooling), the product is peeled off from the OPP film and then wound. And the new heat transfer technology is { OPP film roller }, coating polyurethane on the printing surface of the screen roller }, forming and drying a film by using an oven 1, hot-pressing the film by using a hot-pressing roller, attaching the film to the woven suede or the imitation cotton velvet }, cooling the film, and rolling the film after the product is peeled from the OPP film. In the new heat transfer printing process, the drying temperature of the oven 1 is 65-75 ℃, the heating and drying time of the oven 1 is 30-40s, the processes of quick drying and film forming can be realized without a second section of oven, and compared with the traditional process, the drying time can be shortened by 30-50s. Namely, the quick drying and quick film forming. 2. When the hot press roller is heated and bonded, the hot press roller has better thermal bonding performance in a heating state, and can realize good and firm bonding with the base cloth in a hot pressing state. 3. After leaving the hot-pressing state and cooling, the product can be rapidly crystallized to form a film, and after being separated from an OPP film, the leather-like surface is smooth and resistant to thermal adhesion.
For both the traditional thermal transfer printing process and the new thermal transfer printing process, the polyurethane resin needs to be cooled and then peeled off, namely the polyurethane resin is required to meet the continuous production requirement of peeling off.
Chinese patent CN 106674464a provides a polyurethane resin for coating an OPP film and a preparation method thereof, wherein the polyurethane resin is coated by using the OPP film as a base material and dried, and then the polyurethane resin can be directly wound into a subsequent process for standby without continuous base fabric compounding and release processes, which is suitable for an intermittent production process. However, since both the polyol and the chain extender used in this patent are low crystalline, there is no way to apply them to the above-mentioned new thermal transfer process.
Disclosure of Invention
The invention aims to provide polyurethane resin for thermal transfer printing, which has better thermal bonding performance under the state of heating film formation and realizes good adhesion with base cloth; after cooling, the film can be quickly crystallized and formed, and after being peeled off and separated from the OPP film, the surface is ensured to be smooth and heat-resistant.
The second object of the present invention is to provide a method for producing the polyurethane resin for thermal transfer printing.
It is a further object of the present invention to provide a working slurry.
The fourth object of the present invention is to provide a thermal transfer film.
In order to achieve the above object, the present invention provides the following technical solutions: the polyurethane resin for thermal transfer printing is prepared from the following raw materials: a polyadipic polyester diol, a polyphthalic polyester diol, diphenylmethane-4, 4' -diisocyanate and a solvent.
Preferably, the mass ratio of the polyadipic polyester diol to the polyphthalic polyester diol is 3:7-1:1;
preferably, the number average molecular weight of the polyadipic polyester diol is 2000, and the number average molecular weight of the polyphthalic polyester diol is 2000.
Preferably, the polyurethane resin for thermal transfer printing is prepared from the following raw materials in parts by weight: 13.0 to 27.0 parts of polyadipic acid polyester diol, 22.0 to 37.5 parts of polyphthalic acid polyester diol, 5.5 to 6.7 parts of diphenylmethane-4, 4' -diisocyanate and 40 to 50 parts of solvent;
preferably, the polyadipic acid polyester diol is polyadipic acid-1, 4-butanediol polyester diol, the polyphthalic acid polyester diol is polyphthalic acid-diethylene glycol polyester diol, and the solvent is N, N-dimethylformamide.
In order to achieve the second object, the present invention provides the following technical solutions: the preparation method of the polyurethane resin for thermal transfer printing comprises the following steps:
firstly, putting the poly (adipic acid) polyester diol, the poly (phthalic acid) polyester diol and part of the solvent into a reaction kettle, uniformly mixing, and then, carrying out a second-step reaction;
and secondly, adding the diphenylmethane-4, 4' -diisocyanate into the mixture obtained in the first step in batches, adding the residual solvent after the viscosity value measured at 50 ℃ of the reaction system is 150-250 Pa.s, and stopping the reaction when the viscosity value measured at 20 ℃ of the reaction system is 80-140 Pa.s.
Preferably, the second step is specifically that a first batch of the diphenylmethane-4, 4 '-diisocyanate is added into the mixture obtained in the first step, the temperature is raised to 70-80 ℃, the solid content of the reaction system is 55-62%, the NCO/OH molar ratio=0.80, the reaction is carried out until no NCO residue is detected, the rest of the diphenylmethane-4, 4' -diisocyanate is added, after the viscosity value of the reaction system measured at 50 ℃ is 150-250 Pa.s, the rest of the solvent is added, and the reaction is terminated when the viscosity value of the reaction system measured at 20 ℃ is 80-140 Pa.s again.
In order to achieve the third object, the present invention provides the following technical solutions: a working paste comprising the polyurethane resin for thermal transfer as described above.
Preferably, the working paste further comprises an aliphatic isocyanate trimer, a solvent and a color paste.
Preferably, the aliphatic isocyanate trimer is an HDI trimer and the solvent is butanone.
Preferably, the working paste comprises 100 parts by weight of polyurethane resin for thermal transfer printing, 0-2 parts by weight of aliphatic isocyanate trimer, 90-110 parts by weight of solvent and 5 parts by weight of color paste.
In order to achieve the fourth object, the present invention provides the following technical solutions: the thermal transfer film is prepared by coating the working slurry on a substrate, forming a film and drying.
Preferably, the thermal transfer film is prepared by coating the working slurry on the substrate in a screen roller printing mode, and forming a film and drying.
Preferably, the substrate is an OPP film.
More preferably, the working slurry is applied to the OPP film in a sizing amount of 20-30g/m 2 。
The beneficial effects are that:
the polyurethane resin for thermal transfer printing can have better thermal bonding performance under the state of heating film formation, and realizes good adhesion with base cloth; after cooling, the film can be quickly crystallized and formed, and after being peeled off and separated from the OPP film, the surface is ensured to be smooth and heat-resistant.
The polyurethane resin for thermal transfer printing can meet the requirements of a new thermal transfer printing process (OPP film roller, coating polyurethane on the printing surface of a net roller, forming a film by a baking oven 1, drying, hot pressing by a hot pressing roller, laminating with woven suede or imitation cotton velvet, cooling, and rolling after the product is peeled from the OPP film).
The polyurethane resin for thermal transfer printing can be coated on an OPP film, transferred onto woven suede or imitation cotton velvet by a thermal transfer printing method, used for manufacturing technical cloth, and further used for manufacturing technical cloth sofas.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Aiming at the problem that the existing polyurethane resin cannot meet the requirements of a new thermal transfer printing process (OPP film roller, coating polyurethane on the printing surface of a net roller, forming a film and drying by a baking oven 1, hot pressing and laminating with woven suede or imitation cotton velvet by a hot pressing roller, cooling, namely stripping and rolling after a product is peeled from the OPP film), the invention provides the polyurethane resin for thermal transfer printing, which is prepared from the following raw materials: a polyadipic polyester diol, a polyphthalic polyester diol, diphenylmethane-4, 4' -diisocyanate and a solvent.
According to the polyurethane resin disclosed by the invention, in the technical scheme, the polyurethane resin for forming the thermal transfer printing has excellent thermal adhesiveness through the introduction of the polyester diol of the polyphthalic acid system. When the hot press roller is heated and bonded, the hot press roller has better thermal bonding performance in a heating state, and can realize good and firm bonding with the base cloth in a hot pressing state; by introducing the poly (adipic acid) polyester diol, excellent crystallinity of the polyurethane resin is provided, and after cooling, the polyurethane resin can be rapidly crystallized to form a film, and after being separated from an OPP film, the heat-resistant adhesion of the surface is ensured. The aim of the invention is achieved by the synergistic effect of the poly (phthalic acid) polyester diol and the poly (adipic acid) polyester diol.
In a preferred embodiment of the present invention, the mass ratio of the polyadipic polyester diol to the polyphthalic polyester diol is 3:7 to 1:1 (e.g., 3:7, 4:7, 5:7, 6:7, or 1:1).
In a preferred embodiment of the present invention, the number average molecular weight of the polyadipic polyester diol is 2000, and the number average molecular weight of the polyphthalic polyester diol is 2000.
In a preferred embodiment of the present invention, the polyurethane resin for thermal transfer printing is prepared from the following raw materials in parts by weight: 13.0 to 27.0 parts (e.g., 13.0 parts, 16.0 parts, 19.0 parts, 21.0 parts, 23.0 parts, 25.0 parts, or 27.0 parts), 22.0 to 37.5 parts (e.g., 22.0 parts, 26.0 parts, 30.0 parts, 34.0 parts, or 37.5 parts), 5.5 to 6.7 parts (e.g., 5.5 parts, 5.7 parts, 5.9 parts, 6.1 parts, 6.3 parts, 6.5 parts, or 6.7 parts) of diphenylmethane-4, 4' -diisocyanate, and 40 to 50 parts (e.g., 40 parts, 42 parts, 46 parts, 48 parts, or 50 parts) of solvent.
In a preferred embodiment of the present invention, the polyadipic acid polyester diol is polyadipic acid-1, 4-butanediol polyester diol, the polyphthalic acid polyester diol is polyphthalic acid-diethylene glycol polyester diol, and the solvent is N, N-dimethylformamide. In particular, the rigid structure of benzene ring is contained in the polyethylene glycol polyester diol introduced in the invention, so that the polyurethane resin for thermal transfer printing can meet the hand feeling and hardness requirements of technical cloth sofa without additionally introducing a glycol chain extender as a hard chain segment. Compared with the prior art that a glycol chain extender is conventionally used as a hard chain segment, the system has the characteristic of good initial viscosity after film formation, and even if the solvent volatilizes and dries, the formed polyurethane layer still has good initial viscosity, that is, the polyurethane resin for thermal transfer printing can be thermally bonded in a state that the solvent is basically dried during bonding, and good bonding can be realized. The invention has very important significance for meeting the new heat transfer process (OPP film roller, coating polyurethane on the printing surface of the screen roller, forming film and drying by the oven 1, hot pressing by the hot pressing roller and laminating with tatting suede or imitation cotton velvet, cooling, and rolling after the product is peeled off from the OPP film), namely, the aim of the invention can be realized even though the secondary drying is absent, and further, better heat bonding performance in a heating state and better and firmer adhesion with the base cloth in a hot pressing state are ensured when the hot pressing roller is heated and laminated.
The invention also provides a preparation method of the polyurethane resin for thermal transfer printing, which comprises the following steps: firstly, at room temperature, putting the poly (adipic acid) polyester diol, the phthalic acid polyester diol and part of the solvent into a reaction kettle, uniformly mixing, and then, carrying out a second-step reaction.
And a second step of adding the diphenylmethane-4, 4' -diisocyanate to the mixture obtained in the first step in portions, and terminating the reaction when the viscosity of the reaction system has a viscosity value of 150 to 250 Pa.s (for example, 150 Pa.s, 180 Pa.s, 210 Pa.s, 230 Pa.s, or 250 Pa.s) measured at 50 ℃, adding the remaining solvent, and detecting again that the viscosity of the reaction system has a viscosity value of 80 to 140 Pa.s (for example, 80 Pa.s, 100 Pa.s, 120 Pa.s, 130 Pa.s, or 140 Pa.s) measured at 20 ℃.
In a preferred embodiment of the present invention, the method for preparing polyurethane resin for thermal transfer printing comprises the steps of: specifically, the second step is to add the first batch of the diphenylmethane-4, 4 '-diisocyanate to the mixture obtained in the first step, raise the temperature to 70-80 ℃ (e.g., 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃ or 80 ℃) to make the solid content of the reaction system 55-62% (e.g., 55%, 57%, 59%, 60% or 62%), react until no NCO residues exist, then add the rest of the diphenylmethane-4, 4' -diisocyanate until the viscosity value measured at 50 ℃ of the reaction system is 150-250pa·s (e.g., 150pa·s, 180pa·s, 210pa·s, 230pa·s or 250pa·s), add the rest of the solvent, and again detect the viscosity value measured at 50 ℃ of the reaction system to be 150-250pa·s (e.g., 150pa·s, 180pa·s, 210pa·s, 230pa·s or 250pa·s), and terminate the reaction. According to the invention, the diphenylmethane-4, 4 '-diisocyanate is added twice, so that the regulation of the regularity of the molecular structure generated by the reaction is facilitated, and the production operation control is facilitated compared with the process that the diphenylmethane-4, 4' -diisocyanate is added into the reaction system at one time.
The invention also provides a working slurry which comprises the polyurethane resin for thermal transfer printing.
In a preferred embodiment of the present invention, the working paste further comprises at least one of an aliphatic isocyanate trimer, a solvent and a color paste.
In a preferred embodiment of the present invention, the aliphatic isocyanate trimer is an HDI trimer and the solvent is butanone.
In a preferred embodiment of the present invention, the working paste comprises 100 parts by weight of the polyurethane resin for thermal transfer printing, 0 to 2 parts (for example, 0 part, 0.5 part, 1 part, 1.5 parts or 2 parts) of the aliphatic isocyanate trimer, 90 to 110 parts (for example, 90 parts, 95 parts, 100 parts, 105 parts or 110 parts) of the solvent, and 5 parts of the color paste.
The invention also provides a thermal transfer film, which is prepared by coating the thermal transfer polyurethane resin or the working slurry on a substrate, forming a film and drying.
In a preferred embodiment of the present invention, the thermal transfer film is prepared by coating the thermal transfer polyurethane resin or the working paste described above on the substrate by means of screen roller printing, and film forming and drying.
In a preferred embodiment of the invention, the substrate is an OPP film.
In a preferred embodiment of the present invention, the working slurry is applied to the OPP film in a sizing amount of 20-30g/m 2 (e.g. 20g/m 2 、22g/m 2 、24g/m 2 、26g/m 2 、28g/m 2 Or 30g/m 2 )。
For convenience of writing, the raw materials used in the following examples are abbreviated in English, wherein PE-6 is a poly (1, 4-butylene glycol) -based polyester diol having a number average molecular weight of 2000; HDPOL-320D is a polyphthalate-diethylene glycol based polyester diol having a number average molecular weight of 2000; PE-3320 is poly (neopentyl glycol adipate) glycol with number average molecular weight of 2000 synthesized by polycondensation reaction of adipic acid and neopentyl glycol; MDI is diphenylmethane-4, 4' -diisocyanate; DMF is N, N-dimethylformamide; the HDI trimer is a hexamethylene diisocyanate trimer.
Example 1:
the polyurethane resin for thermal transfer printing of this example was prepared from the following raw materials in parts by weight (as shown in table 1 below):
table 1 raw material composition of polyurethane resin for thermal transfer of example 1
| Raw materials | Parts by weight |
| PE-6 | 133.5 |
| HDPOL-320D | 311.5 |
| MDI | 55.6 |
| DMF | 500.6 |
The polyurethane resin for thermal transfer of example 1 was realized by the following process:
a preparation method of polyurethane resin for thermal transfer printing comprises the following steps:
step 1:
putting 133.5 parts of PE-6, 311.5 parts of HDPOL-320D and 400.5 parts of N, N-dimethylformamide calculated according to the solid content (solid content of 55%) into a reaction kettle, and uniformly mixing;
step 2:
firstly, adding 44.5 parts of MDI into the mixture obtained by the treatment in the step 1, heating to a temperature range of 70 ℃ for reaction, wherein the solid content is controlled to be 55%, and NCO/OH=0.80; reacting until no NCO residue exists by detection;
and adding 11.1 parts of residual diphenylmethane-4, 4' -diisocyanate into the reaction system, after the viscosity of the reaction system is 200 Pa.s, adding 100.1 parts of N, N-dimethylformamide, and stopping the reaction when the viscosity of the reaction system is 120 Pa.s, thus obtaining the polyurethane resin for thermal transfer printing of the example 1.
Example 2:
the polyurethane resin for thermal transfer printing of this example was prepared from the following raw materials in parts by weight (as shown in table 2 below):
TABLE 2 raw material composition of polyurethane resin for thermal transfer of example 2
The polyurethane resin for thermal transfer of example 2 was realized by the following process:
a preparation method of polyurethane resin for thermal transfer printing comprises the following steps:
step 1:
adding 222.5 parts of PE-6, 222.5 parts of HDPOL-320D and 400.5 parts of N, N-dimethylformamide calculated according to the solid content (solid content is 55%) into a reaction kettle, and uniformly mixing;
step 2:
firstly, adding 44.5 parts of MDI into the mixture obtained by the treatment in the step 1, heating to a temperature range of 80 ℃ for reaction, wherein the solid content is controlled to be 55%, and NCO/OH=0.80; reacting until no NCO residue exists by detection;
and adding 11.1 parts of residual diphenylmethane-4, 4' -diisocyanate into the reaction system, after the viscosity of the reaction system is measured to be 250 Pa.s at 50 ℃, adding the residual 100.1 parts of N, N-dimethylformamide, and stopping the reaction when the viscosity of the reaction system is measured to be 136 Pa.s at 20 ℃, thus obtaining the polyurethane resin for thermal transfer printing in the example 2.
Example 3:
the polyurethane resin for thermal transfer printing of this example was prepared from the following raw materials in parts by weight (as shown in table 3 below):
TABLE 3 raw material composition of polyurethane resin for thermal transfer of example 3
| Raw materials | Parts by weight |
| PE-6 | 147 |
| HDPOL-320D | 343 |
| MDI | 61.3 |
| DMF | 451.1 |
The polyurethane resin for thermal transfer of example 3 was realized by the following process:
a method for preparing polyurethane resin, comprising the following steps:
step 1:
147 parts of PE-6, 343 parts of HDPOL-320D and 359.3 parts of N, N-dimethylformamide calculated according to solid content (solid content is 60%) are put into a reaction kettle and uniformly mixed;
step 2:
firstly, adding 49 parts of MDI into the mixture obtained by the treatment in the step 1, heating to a temperature range of 75 ℃ for reaction, wherein the solid content is controlled to be 60%, and NCO/OH=0.80; reacting until no NCO residue exists by detection;
and then adding 12.3 parts of residual diphenylmethane-4, 4' -diisocyanate into the reaction system, after the viscosity of the reaction system is measured to be 170 Pa.s at 50 ℃, adding the residual 91.8 parts of N, N-dimethylformamide, and stopping the reaction when the viscosity of the reaction system is measured to be 88 Pa.s at 20 ℃, thus obtaining the polyurethane resin for thermal transfer printing of the example 3.
Example 4:
the polyurethane resin for thermal transfer printing of this example was prepared from the following raw materials in parts by weight (as shown in table 4 below):
TABLE 4 raw material composition of polyurethane resin for thermal transfer of example 4
| Raw materials | Parts by weight |
| PE-6 | 245 |
| HDPOL-320D | 245 |
| MDI | 61.3 |
| DMF | 451.1 |
The polyurethane resin for thermal transfer of example 4 was realized by the following process:
a preparation method of polyurethane resin for thermal transfer printing comprises the following steps:
step 1:
putting 245 parts of PE-6, 245 parts of HDPOL-320D and 359.3 parts of N, N-dimethylformamide calculated according to solid content (solid content is 60%) into a reaction kettle, and uniformly mixing;
step 2:
firstly, adding 49 parts of MDI into the mixture obtained by the treatment in the step 1, heating to a temperature range of 70 ℃ for reaction, wherein the solid content is controlled to be 60%, and NCO/OH=0.80; reacting until no NCO residue exists by detection;
and then adding 12.3 parts of residual diphenylmethane-4, 4' -diisocyanate into the reaction system, after the viscosity value of the reaction system measured at 50 ℃ is 220 Pa.s, adding the residual 91.8 parts of N, N-dimethylformamide, and stopping the reaction when the viscosity value of the reaction system measured at 20 ℃ is 128 Pa.s, thus obtaining the polyurethane resin for thermal transfer printing of the example 4.
Example 5:
the polyurethane resin for thermal transfer printing of this example was prepared from the following raw materials in parts by weight (as shown in table 5 below):
TABLE 5 raw material composition of polyurethane resin for thermal transfer of example 5
| Raw materials | Parts by weight |
| PE-6 | 160.5 |
| HDPOL-320D | 374.5 |
| MDI | 66.9 |
| DMF | 401.2 |
The polyurethane resin for thermal transfer of example 5 was realized by the following process:
a preparation method of polyurethane resin for thermal transfer printing comprises the following steps:
step 1:
putting 160.5 parts of PE-6, 374.5 parts of HDPOL-320D and 360.7 parts of N, N-dimethylformamide calculated according to solid content (solid content is 62%) into a reaction kettle, and uniformly mixing;
step 2:
firstly, 53.5 parts of MDI is added into the mixture obtained by the treatment in the step 1, the temperature is raised to 70 ℃ for reaction, the solid content is controlled at 62%, and NCO/OH=0.80; reacting until no NCO residue exists by detection;
13.4 parts of residual diphenylmethane-4, 4' -diisocyanate was then added to the reaction system, and after the viscosity of the reaction system was found to be 200 Pa.s at 50 ℃, 40.5 parts of N, N-dimethylformamide was added thereto, and when the viscosity of the reaction system was found to be 116 Pa.s at 20 ℃, the reaction was terminated to obtain a polyurethane resin for thermal transfer printing of example 5.
Example 6:
the polyurethane resin for thermal transfer printing of this example was prepared from the following raw materials in parts by weight (as shown in table 6 below):
TABLE 6 raw material composition of polyurethane resin for thermal transfer of example 6
| Raw materials | Parts by weight |
| PE-6 | 222.9 |
| HDPOL-320D | 312.1 |
| MDI | 66.9 |
| DMF | 401.2 |
The polyurethane resin for thermal transfer of example 6 was obtained by the following process:
a preparation method of polyurethane resin for thermal transfer printing comprises the following steps:
step 1:
222.9 parts of PE-6, 312.1 parts of HDPOL-320D and 360.7 parts of N, N-dimethylformamide calculated according to the solid content (the solid content is 62%) are put into a reaction kettle and uniformly mixed;
step 2:
firstly, 53.5 parts of MDI is added into the mixture obtained by the treatment in the step 1, the temperature is raised to 70 ℃ for reaction, the solid content is controlled at 62%, and NCO/OH=0.80; reacting until no NCO residue exists by detection;
13.4 parts of residual diphenylmethane-4, 4' -diisocyanate was then added to the reaction system, and after the viscosity of the reaction system had been found to be 230 Pa.s at 50 ℃, 40.5 parts of N, N-dimethylformamide was added thereto, and the reaction was terminated when the viscosity of the reaction system had been found to be 108 Pa.s at 20 ℃, to obtain a polyurethane resin for thermal transfer printing of example 6.
Comparative example 1:
the polyurethane resin for thermal transfer printing of this comparative example was prepared from the following raw materials in parts by weight (as shown in table 7 below):
TABLE 7 raw material composition of polyurethane resin for thermal transfer of example 7
The polyurethane resin for thermal transfer of comparative example 1 was obtained by the following process:
a preparation method of polyurethane resin for thermal transfer printing comprises the following steps:
step 1:
535 parts of PE-6 and 360.7 parts of N, N-dimethylformamide calculated according to the solid content are put into a reaction kettle and uniformly mixed;
step 2:
firstly, 53.5 parts of MDI is added into the mixture obtained by the treatment in the step 1, the temperature is raised to 70 ℃ for reaction, the solid content is controlled at 62%, and NCO/OH=0.80; reacting until no NCO residue exists by detection;
and adding 13.4 parts of residual diphenylmethane-4, 4' -diisocyanate into the reaction system, adding the residual 40.5 parts of N, N-dimethylformamide after the viscosity value of the reaction system measured at 50 ℃ is 200 Pa.s, and stopping the reaction when the viscosity value of the reaction system measured at 20 ℃ is 116 Pa.s, thus obtaining the polyurethane resin for thermal transfer printing of the comparative example 1.
Comparative example 2:
the polyurethane resin for thermal transfer printing of this comparative example was prepared from the following raw materials in parts by weight (as shown in table 8 below):
TABLE 8 raw material composition of polyurethane resin for thermal transfer of example 8
| Raw materials | Parts by weight |
| HDPOL-320D | 535 |
| MDI | 66.9 |
| DMF | 401.2 |
The polyurethane resin for thermal transfer of comparative example 2 was obtained by the following process:
a preparation method of polyurethane resin for thermal transfer printing comprises the following steps:
step 1:
535 parts of HDPOL-320D and 360.7 parts of N, N-dimethylformamide calculated according to the solid content are put into a reaction kettle and uniformly mixed;
step 2:
firstly, 53.5 parts of MDI is added into the mixture obtained by the treatment in the step 1, and then the mixture reacts at the temperature range of 70 ℃, wherein the solid content is controlled to be 62%, and NCO/OH=0.80; reacting until no NCO residue exists by detection;
13.4 parts of residual diphenylmethane-4, 4' -diisocyanate was then added to the reaction system, and after the viscosity of the reaction system had been found to be 200 Pa.s at 50 ℃, 40.5 parts of N, N-dimethylformamide was added thereto, and the reaction was terminated when the viscosity of the reaction system had been found to be 120 Pa.s at 20 ℃, to thereby obtain a polyurethane resin for thermal transfer printing of comparative example 2.
Comparative example 3
The only difference from example 5 is that: the weight ratio of PE-6 to HDPOL-320D was 2:7, the remainder being identical to example 5.
Comparative example 4
The only difference from example 5 is that: the weight ratio of PE-6 to HDPOL-320D was 8:7, the remainder being identical to example 5.
Comparative example 5
The polyurethane resin for thermal transfer printing of this comparative example was prepared from the following raw materials in parts by weight (as shown in table 9 below):
table 9 raw material composition of polyurethane resin for thermal transfer of comparative example 5
| Raw materials | Parts by weight |
| PE-6 | 230 |
| PE-3320 | 230 |
| EG (ethylene glycol) | 2.61 |
| MDI | 68.0 |
| DMF | 531 |
The polyurethane resin for thermal transfer of comparative example 5 was obtained by the following process:
a preparation method of polyurethane resin for thermal transfer printing comprises the following steps:
step 1:
230 parts of PE-6, 230 parts of PE-3320 and 2.61 parts of EG (ethylene glycol) are put into a reaction kettle and uniformly mixed, wherein 423 parts of N, N-dimethylformamide are calculated according to solid content (solid content is 55 percent);
step 2:
firstly, 54.4 parts of MDI is added into the mixture obtained by the treatment in the step 1, the temperature is raised to 80 ℃ for reaction, the solid content is controlled to 55%, and NCO/OH=0.80; reacting until no NCO residue exists by detection;
and adding 13.6 parts of residual diphenylmethane-4, 4' -diisocyanate into the reaction system, adding the residual 108 parts of N, N-dimethylformamide after the viscosity value of the reaction system measured at 50 ℃ is 250 Pa.s, and stopping the reaction when the viscosity value of the reaction system measured at 20 ℃ is 136 Pa.s, thus obtaining the polyurethane resin for thermal transfer printing of the comparative example 5.
The polyurethane resins for thermal transfer of examples 1 to 6, the resins numbered 1 to 6, the polyurethane resins for thermal transfer of comparative examples 1 to 5, the resins numbered 7 to 11, were diluted with 100 parts of butanone into solutions having viscosities of 500 to 1000CPS/25℃respectively, and 5 parts of brown syrup was added to the diluted solutions, and 0% to 2% of aliphatic isocyanate trimer (HDI trimer) was added to the example or comparative example resins. No. A of HDI trimer was added (i.e., 0%) and No. B of 2% HDI trimer was added, and the diluted solutions were 1A syrup, 1B syrup … …, and up to 11A syrup, 11B syrup.
The working slurries 1A,1B,2A,2B,3A,3B,4A,4B,5A,5B,6A,6B,7A,7B,8A,8B,9A,9B,10A,10B,11A,11B were mixed at 20g/m 2 Sizing, coating on an OPP film in a screen roller printing mode, sizing by a new thermal transfer process (OPP film roller, coating polyurethane on the screen roller printing surface, drying by forming a film in an oven 1, hot pressing by a hot pressing roller, laminating with tatting suede or imitation cotton velvet, cooling, and rolling after peeling off the product from the OPP film), wherein tatting suede is used as a base cloth for lamination; the adhesion of the resin layer to the suede after separation from the OPP film was compared, as well as the hot tack resistance and surface smoothness of the leather-like.
Wherein, after finishing the fastness test, taking a 20cm multiplied by 20cm leather sample, sticking the leather sample on the surface of the leather sample by using a transparent adhesive tape, tearing off the leather sample, and comparing the staining condition of the adhesive tape; the heat-resistant adhesion test is to take a 20cm multiplied by 20cm leather sample after rolling, fold the leather sample in half, place the leather sample under two glass plates, place the leather sample in an oven at 100 ℃, load 3 kg on the glass plates, and compare whether the folded leather sample surface layers can be successfully separated after 2 hours, thereby evaluating the difference of the heat-resistant adhesion of the leather sample. The experimental results are shown in table 10 below:
table 10 Performance of leather samples treated with polyurethane resin for thermal transfer of examples 1 to 6 and comparative examples 1 to 4
As can be seen from table 10:
1. the 1A,1B,2A,2B,3A,3B,4A,4B,5A,5B,6A,6B working slurries corresponding to examples 1-6 can be used for sizing in a new thermal transfer printing process, and have better adhesive fastness and heat-resistant viscosity. Meanwhile, compared with A, the addition of the HDI trimer can improve the adhesion fastness.
2. Comparative examples 1-comparative example 2 corresponding to the working slurries 7a,7b,8a,8b, when sized using a new thermal transfer process, exhibited poor adhesion and thus were not suitable for use in a new thermal transfer process. Although the addition of HDI trimer in B can properly improve the adhesion, it cannot change the result that it cannot be applied to new thermal transfer sizing.
3. Comparative example 3, 9A,9B, uses too much HDPOL-320D, and thus improves adhesion, but has poor hot tack resistance. Comparative example 4, 10A,10B, has improved heat resistance due to excessive use of PE-6. However, since both are not in the optimal range, the solutions of comparative example 3 and comparative example 4 fail to meet the requirements of the new thermal transfer process.
4. When the new thermal transfer process is used for sizing 11a and 11b corresponding to comparative example 5, the defect of poor adhesion occurs, and the requirement of the new thermal transfer process cannot be met.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The polyurethane resin for thermal transfer printing is characterized by being prepared from the following raw materials: a polyadipic polyester diol, a polyphthalic polyester diol, diphenylmethane-4, 4' -diisocyanate and a solvent;
the polyadipic acid polyester diol is polyadipic acid-1, 4-butanediol polyester diol, and the polyphthalic acid polyester diol is polyphthalic acid-diethylene glycol polyester diol;
the mass ratio of the polyadipic acid polyester diol to the polyphthalic acid polyester diol is 3:7-1:1;
the polyurethane resin for thermal transfer printing is prepared by a method comprising the following steps:
firstly, putting the poly (adipic acid) polyester diol, the poly (phthalic acid) polyester diol and part of the solvent into a reaction kettle, uniformly mixing, and then, carrying out a second-step reaction;
and secondly, adding a first batch of the diphenylmethane-4, 4 '-diisocyanate into the mixture obtained in the first step, heating to 70-80 ℃, reacting until the solid content of a reaction system is 55-62%, the NCO/OH molar ratio=0.80 until no NCO residue is detected, adding the rest of the diphenylmethane-4, 4' -diisocyanate, adding the rest of the solvent after the viscosity value of the reaction system measured at 50 ℃ is 150-250 Pa.s, and stopping the reaction when the viscosity value of the reaction system measured at 20 ℃ is 80-140 Pa.s.
2. The polyurethane resin for thermal transfer according to claim 1, wherein the number average molecular weight of the polyadipic acid-based polyester diol is 2000 and the number average molecular weight of the polyphthalic acid-based polyester diol is 2000.
3. The polyurethane resin for thermal transfer according to claim 1, wherein the solvent is N, N-dimethylformamide.
4. A method for producing a polyurethane resin for thermal transfer according to any one of claims 1 to 3, comprising the steps of:
firstly, putting the poly (adipic acid) polyester diol, the poly (phthalic acid) polyester diol and part of the solvent into a reaction kettle, uniformly mixing, and then, carrying out a second-step reaction;
and secondly, adding a first batch of the diphenylmethane-4, 4 '-diisocyanate into the mixture obtained in the first step, heating to 70-80 ℃, reacting until the solid content of a reaction system is 55-62%, the NCO/OH molar ratio=0.80 until no NCO residue is detected, adding the rest of the diphenylmethane-4, 4' -diisocyanate, adding the rest of the solvent after the viscosity value of the reaction system measured at 50 ℃ is 150-250 Pa.s, and stopping the reaction when the viscosity value of the reaction system measured at 20 ℃ is 80-140 Pa.s.
5. A working slurry comprising the polyurethane resin for thermal transfer according to any one of claims 1 to 3.
6. The working slurry of claim 5 further comprising an aliphatic isocyanate trimer, a solvent and color paste.
7. The working slurry of claim 6 wherein the aliphatic isocyanate trimer is HDI trimer and the solvent is butanone.
8. The working paste according to claim 6, wherein the working paste comprises 100 parts by weight of the polyurethane resin for thermal transfer printing, 0-2 parts by weight of the aliphatic isocyanate trimer, 90-110 parts by weight of the solvent and 5 parts by weight of the color paste.
9. A thermal transfer film, wherein the thermal transfer film is prepared by coating the working slurry according to any one of claims 6 to 8 on a substrate, and drying the film.
10. The thermal transfer film according to claim 9, wherein the thermal transfer film is prepared by applying the working paste according to any one of claims 6 to 8 to the substrate by screen roller printing, film-forming and drying;
the substrate is an OPP film; the working slurry is coated onWhen the OPP film is coated, the sizing amount is 20-30g/m 2 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111530467.3A CN114316178B (en) | 2021-12-14 | 2021-12-14 | Polyurethane resin for thermal transfer printing, preparation method thereof, working slurry and thermal transfer printing film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111530467.3A CN114316178B (en) | 2021-12-14 | 2021-12-14 | Polyurethane resin for thermal transfer printing, preparation method thereof, working slurry and thermal transfer printing film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114316178A CN114316178A (en) | 2022-04-12 |
| CN114316178B true CN114316178B (en) | 2023-10-24 |
Family
ID=81050030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111530467.3A Active CN114316178B (en) | 2021-12-14 | 2021-12-14 | Polyurethane resin for thermal transfer printing, preparation method thereof, working slurry and thermal transfer printing film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114316178B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1071930A (en) * | 1965-03-17 | 1967-06-14 | Bayer Ag | Improvements relating to lacquer solutions |
| JP2010194885A (en) * | 2009-02-25 | 2010-09-09 | Kao Corp | Dye receiving layer composition |
| CN102286262A (en) * | 2011-07-12 | 2011-12-21 | 厦门大学 | Method for preparing polyurethane hot melting transfer print glue |
| CN104356916A (en) * | 2014-11-21 | 2015-02-18 | 广东华江粉末科技有限公司 | High-gloss polyurethane heat transfer printing powder paint for aluminium profile and preparation method thereof |
| CN105916947A (en) * | 2014-01-17 | 2016-08-31 | 巴斯夫欧洲公司 | Lamination printing ink comprising an aqueous dispersion comprising polyurethane |
| CN106459350A (en) * | 2014-05-16 | 2017-02-22 | 汉高股份有限及两合公司 | Thermoplastic polyurethane |
| CN108610467A (en) * | 2018-04-11 | 2018-10-02 | 高鼎精细化工(昆山)有限公司 | One-way type solvent-free polyurethane resin, the dermatine containing the resin and its manufacturing method |
| CN108997741A (en) * | 2018-07-09 | 2018-12-14 | 东莞市鼎盛塑胶膜有限公司 | It is a kind of to turn elastic membrane and preparation method thereof entirely |
| CN110256998A (en) * | 2019-06-14 | 2019-09-20 | 南通天洋新材料有限公司 | A kind of preparation method of moisture-curable polyurethane hot melt adhesive |
| CN111117548A (en) * | 2018-10-30 | 2020-05-08 | 浙江华峰热塑性聚氨酯有限公司 | Thermoplastic polyurethane adhesive and preparation thereof |
| CN111423837A (en) * | 2020-04-08 | 2020-07-17 | 上海抚佳精细化工有限公司 | TPU hot melt adhesive and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002004536A2 (en) * | 2000-07-12 | 2002-01-17 | Uniroyal Chemical Company, Inc. | Modified urethane compositions containing adducts of o-phthalic anhydride ester polyols |
| US6953624B2 (en) * | 2001-03-02 | 2005-10-11 | 3M Innovative Properties Company | Printable film and coating composition exhibiting stain resistance |
| EP2944661B1 (en) * | 2014-05-16 | 2019-09-18 | Henkel AG & Co. KGaA | Thermoplastic polyurethane hot melt adhesive |
| US11396575B2 (en) * | 2019-09-19 | 2022-07-26 | Sunko Ink Co., Ltd. | Polyester polyol, thermoplastic polyurethane and article thereof |
-
2021
- 2021-12-14 CN CN202111530467.3A patent/CN114316178B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1071930A (en) * | 1965-03-17 | 1967-06-14 | Bayer Ag | Improvements relating to lacquer solutions |
| JP2010194885A (en) * | 2009-02-25 | 2010-09-09 | Kao Corp | Dye receiving layer composition |
| CN102286262A (en) * | 2011-07-12 | 2011-12-21 | 厦门大学 | Method for preparing polyurethane hot melting transfer print glue |
| CN105916947A (en) * | 2014-01-17 | 2016-08-31 | 巴斯夫欧洲公司 | Lamination printing ink comprising an aqueous dispersion comprising polyurethane |
| CN106459350A (en) * | 2014-05-16 | 2017-02-22 | 汉高股份有限及两合公司 | Thermoplastic polyurethane |
| CN104356916A (en) * | 2014-11-21 | 2015-02-18 | 广东华江粉末科技有限公司 | High-gloss polyurethane heat transfer printing powder paint for aluminium profile and preparation method thereof |
| CN108610467A (en) * | 2018-04-11 | 2018-10-02 | 高鼎精细化工(昆山)有限公司 | One-way type solvent-free polyurethane resin, the dermatine containing the resin and its manufacturing method |
| CN108997741A (en) * | 2018-07-09 | 2018-12-14 | 东莞市鼎盛塑胶膜有限公司 | It is a kind of to turn elastic membrane and preparation method thereof entirely |
| CN111117548A (en) * | 2018-10-30 | 2020-05-08 | 浙江华峰热塑性聚氨酯有限公司 | Thermoplastic polyurethane adhesive and preparation thereof |
| CN110256998A (en) * | 2019-06-14 | 2019-09-20 | 南通天洋新材料有限公司 | A kind of preparation method of moisture-curable polyurethane hot melt adhesive |
| CN111423837A (en) * | 2020-04-08 | 2020-07-17 | 上海抚佳精细化工有限公司 | TPU hot melt adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 基于水性PU/PA、PUA热转印胶的制备与应用研究;凡宇;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》(第01期);B016-1169 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114316178A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102406170B1 (en) | Eco-friendly artificial leather for interior of automobile and manufacturing method thereof | |
| CN107604685A (en) | A kind of preparation method of high temperature resistant color inhibition no-solvent polyurethane synthetic leather | |
| CN108329452B (en) | Non-yellowing solvent-free polyurethane bonding layer resin for synthetic leather and preparation method and application thereof | |
| US20060249244A1 (en) | Method for producing environmental friendly artificial leather product | |
| KR100389934B1 (en) | Aqueous dry laminate adhesive composition for synthetic leather and manufacturing method for synthetic leather using the same | |
| CN105061722A (en) | Waterborne polyurethane resin | |
| CN103073692A (en) | Producing method of water-base polyurethane | |
| CN111944111A (en) | Aqueous self-extinction polyurethane dispersion, preparation method and composition thereof | |
| CN109880069B (en) | Preparation method and application of hydrophilic oligomer dihydric alcohol and solvent-free polyurethane surface layer resin for waterproof moisture-permeable synthetic leather | |
| CN114316178B (en) | Polyurethane resin for thermal transfer printing, preparation method thereof, working slurry and thermal transfer printing film | |
| JP4257564B2 (en) | Aqueous dry laminate adhesive composition for synthetic leather and method for producing synthetic leather using the same | |
| JP4403684B2 (en) | Aqueous dry laminate adhesive composition for synthetic leather and method for producing synthetic leather using the same | |
| KR101322761B1 (en) | The manufacturing method of polyurethane coating resin composition | |
| TWI794284B (en) | Manufacturing method of synthetic leather | |
| JPH023466A (en) | Coating method | |
| CN108914609A (en) | A kind of massage armchair is with laying one's hand on solvent-free PU leather of skin and preparation method thereof | |
| CN110670376B (en) | Solvent-free three-proofing synthetic leather and manufacturing method thereof | |
| CN1843756A (en) | Multi-layered polyurethane film fabric having antibacterial and antimold function and method for manufacturing the same | |
| JP2574004B2 (en) | Synthetic leather with excellent texture | |
| JPH108383A (en) | Production of highly durable synthetic leather with thermoplastic polyurethane resin having excellent solubility | |
| CN111269684B (en) | PU adhesive for double-layer super-ciliated towel cloth and preparation method thereof | |
| CN114891431B (en) | Artificial leather surface treating agent for injection molding and preparation method thereof | |
| CN115057990B (en) | Polyurethane resin for adhesive layer and preparation method and application thereof | |
| WO2023214494A1 (en) | Moisture-curable urethane hot melt resin composition, multilayer body and synthetic artificial leather | |
| CN117362614A (en) | Bio-based oligomer polyol and bio-based solvent-free polyurethane resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |