CN114316178A - 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
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- CN114316178A CN114316178A CN202111530467.3A CN202111530467A CN114316178A CN 114316178 A CN114316178 A CN 114316178A CN 202111530467 A CN202111530467 A CN 202111530467A CN 114316178 A CN114316178 A CN 114316178A
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- thermal transfer
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- polyurethane resin
- transfer printing
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 100
- 238000010023 transfer printing Methods 0.000 title claims abstract description 77
- 239000002002 slurry Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229920000728 polyester Polymers 0.000 claims abstract description 51
- 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
- 150000002009 diols Chemical class 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 229920005586 poly(adipic acid) Polymers 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 82
- 238000006243 chemical reaction Methods 0.000 claims description 80
- 238000000034 method Methods 0.000 claims description 46
- 238000012546 transfer Methods 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 aliphatic isocyanate Chemical class 0.000 claims description 11
- 239000012948 isocyanate Substances 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
- 239000013638 trimer Substances 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 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 5
- 239000013557 residual solvent Substances 0.000 claims description 4
- 150000001279 adipic acids Chemical class 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Substances OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 150000003022 phthalic acids Chemical class 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 abstract description 23
- 238000001816 cooling Methods 0.000 abstract description 16
- BKUKXOMYGPYFJJ-UHFFFAOYSA-N 2-ethylsulfanyl-1h-benzimidazole;hydrobromide Chemical compound Br.C1=CC=C2NC(SCC)=NC2=C1 BKUKXOMYGPYFJJ-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001278 adipic acid derivatives Chemical class 0.000 abstract 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 abstract 1
- 230000008569 process Effects 0.000 description 38
- 238000007731 hot pressing Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 23
- 101000573147 Arabidopsis thaliana Pectinesterase 6 Proteins 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- 239000010985 leather Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
- 238000010020 roller printing Methods 0.000 description 7
- 238000004513 sizing Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- SJNWVJGWEJCMEY-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;phthalic acid Chemical compound OCCOCCO.OC(=O)C1=CC=CC=C1C(O)=O SJNWVJGWEJCMEY-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010030 laminating Methods 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
- 238000007639 printing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001481789 Rupicapra Species 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
- 238000013329 compounding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 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
- 238000000643 oven drying Methods 0.000 description 1
- 239000003973 paint Substances 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
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011527 polyurethane coating Substances 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
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000009965 tatting Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of polyurethane resin, and particularly relates to polyurethane resin for thermal transfer printing, a preparation method of the polyurethane resin, working slurry and a thermal transfer printing film. The polyurethane resin for thermal transfer printing is prepared from the following raw materials: a polyester diol of poly adipic acid series, a polyester diol of poly phthalic acid series, diphenylmethane-4, 4' -diisocyanate and a solvent. The polyurethane resin for thermal transfer printing has good thermal bonding performance in a heating film forming state, and realizes good adhesion with base cloth; after cooling, the product can be quickly crystallized to form a film, and after being peeled and separated from the OPP film, the surface is smooth and is anti-hot sticking.
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 of the polyurethane resin, working slurry and a thermal transfer printing film.
Background
The technical cloth is a novel sofa fabric and is known as 'fabric capable of breathing'. Because the fabric has the texture and color of genuine leather and the excellent air permeability of the cloth sofa, the fabric is popular with environment-friendly connoisseurs and animal protectors once being launched, and the technical cloth sofa is 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 the OPP film is finally transferred onto a base cloth (generally woven suede or cotton-like velvet is used) through a thermal transfer printing mode to form a technical cloth sofa fabric.
The conventional thermal transfer process is as follows:
an OPP film roller → a screen roller printing surface coated with polyurethane → an oven 1 for film forming and drying → a hot pressing roller for hot pressing and tatting chamois flannel or cotton-like flannel bonding → an oven 2 for drying-cooling → (product) from the OPP film, namely peeling and rolling.
According to the traditional thermal transfer printing process flow, the whole production process is dried by using two drying ovens, the first drying is to dry the solvent in the polyurethane working slurry out to form a film, then the film is heated and attached through a hot pressing roller, the second drying oven is to dry the residual solvent, and the residual solvent is peeled and wound from the OPP film after being cooled by a cooling roller.
In order to further improve the production efficiency, the current synthetic leather practitioner tries to use a new thermal transfer process, which is as follows:
OPP film roller → net roller printing surface coating polyurethane → oven 1 film forming drying → hot press roller hot pressing and woven suede or cotton-like velvet laminating → cooling → product peeling from OPP film and rolling.
Compared with the traditional process, in the new heat transfer printing process, after hot pressing of the hot pressing roller is laminated with the woven suede nap or the cotton-like nap (short for technical cloth), secondary drying of an oven is not needed, direct cooling and winding are performed, one-time oven drying is omitted, energy is saved, and meanwhile 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 adhesion fastness with the base cloth is good during the thermal transfer printing after film forming, the heat resistance viscosity of the surface is good and the smoothness is good after the second drying and the peeling from the OPP film, the resin can meet the requirement of the traditional thermal transfer printing process on the polyurethane resin.
For the new thermal transfer printing process, because the process of secondary drying is lacked, the polyurethane resin for surface coating is required to be used, and the polyurethane resin can be dried quickly after hot-pressing and attaching by a hot-pressing roller, the polyurethane resin is required to have the following characteristics besides the performances of good adhesion, good heat-resistant viscosity and good smoothness of the polyurethane resin used in the traditional thermal transfer printing process: 1. the paint can be quickly dried in a short time and quickly formed into a film; in the prior art, an OPP film roller → a screen roller printing surface is coated with polyurethane → an oven 1 is used for film forming and drying → a hot pressing roller is used for hot pressing and is attached with woven suede or cotton-like suede → an oven 2 is used for drying-cooling → (products) from the OPP film, namely, the products are peeled off and then wound. In the technology, the drying temperature of the oven 1 is 65-75 ℃, and the heating and drying time of the oven 1 is 40-60 s; the drying temperature of the oven 2 is 65-75 ℃, and the heating and drying time of the oven 2 is 20-30 s. After being dried by a two-section oven and cooled (namely cooled by a cooling roller), the product is peeled off from the OPP film and then is rolled. The new thermal transfer technique is that { OPP film roller → screen roller printing surface coating polyurethane → oven 1 drying of film forming → hot press roller hot pressing and laminating woven suede or cotton-like suede → cooling → (product) peeling off from OPP film and then rolling }. In the new thermal 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 process of quick drying and film forming can be realized without a second-stage oven, and the drying time can be shortened by 30-50s compared with the traditional process. Namely, the rapid drying and the rapid film forming. 2. When the hot-pressing roller is heated and bonded, the hot-pressing roller has better thermal bonding performance in a heating state, and can be well and firmly bonded with the base cloth in a hot-pressing state. 3. After leaving the hot-pressing state and cooling, the film can be quickly crystallized to form a film, and after being separated from the OPP film, the leather-like surface is smooth and is anti-hot-sticking.
In both the traditional thermal transfer printing process and the new thermal transfer printing process, the polyurethane resin is required to be cooled and then to be stripped, namely the polyurethane resin is required to meet the continuous production requirement of stripping.
Chinese patent CN 106674464a provides a polyurethane resin for coating an OPP film and a preparation method thereof, after the OPP film is adopted as a substrate to coat the polyurethane resin and is dried, the OPP film can be directly rolled into a subsequent process for standby without a continuous base fabric compounding and releasing process, and the method is suitable for an intermittent production process. However, since the polyol and the chain extender used in this patent are both low in crystallinity, there is no way to apply them to the above-mentioned new thermal transfer process.
Disclosure of Invention
An object of the present invention is to provide a polyurethane resin for thermal transfer which has good thermal adhesion properties in a heated film-forming state and can be well adhered to a base fabric; after cooling, the product can be quickly crystallized to form a film, and after being peeled and separated from the OPP film, the surface is smooth and is anti-hot sticking.
The second object of the present invention is to provide a method for producing the polyurethane resin for thermal transfer.
The invention also aims to provide the working slurry.
The fourth object of the present invention is to provide a thermal transfer film.
In order to achieve the above purpose, the invention provides the following technical scheme: the polyurethane resin for thermal transfer printing is prepared from the following raw materials: a polyester diol of poly adipic acid series, a polyester diol of poly phthalic acid series, diphenylmethane-4, 4' -diisocyanate and a solvent.
Preferably, the mass ratio of the poly adipic acid polyester diol to the poly phthalic acid polyester diol is 3:7-1: 1;
preferably, the number average molecular weight of the polyadipate polyester diol is 2000, and the number average molecular weight of the polyphthalate polyester diol is 2000.
Preferably, the polyurethane resin for thermal transfer printing is prepared by adopting the following raw materials in parts by weight: 13.0-27.0 parts of poly adipic acid polyester dihydric alcohol, 22.0-37.5 parts of poly phthalic acid polyester dihydric alcohol, 5.5-6.7 parts of diphenylmethane-4, 4' -diisocyanate and 40-50 parts of solvent;
preferably, the polyadipic acid polyester diol is polyadipic acid-1, 4-butanediol polyester diol, the polyphthalate polyester diol is polyphthalate-diethylene glycol polyester diol, and the solvent is N, N-dimethylformamide.
In order to achieve the second purpose, the invention provides the following technical scheme: the preparation method of the polyurethane resin for thermal transfer printing comprises the following steps:
firstly, putting the poly adipic acid polyester dihydric alcohol, the poly phthalic acid polyester dihydric alcohol and part of the solvent into a reaction kettle, uniformly mixing, and then carrying out a second step of 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 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 detected again to be 80-140 Pa.s.
Preferably, the second step is specifically, adding a first batch of the diphenylmethane-4, 4 '-diisocyanate into the mixture obtained in the first step, heating to 70-80 ℃, so that the solid content of the reaction system is 55-62%, and the molar ratio of NCO/OH is 0.80, reacting 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 Pa.s, and stopping the reaction when the viscosity value of the reaction system measured at 20 ℃ is 80-140 Pa.s.
In order to achieve the third purpose, the invention provides the following technical scheme: a working slurry comprising the polyurethane resin for thermal transfer printing as described above.
Preferably, the working slurry also comprises aliphatic isocyanate tripolymer, solvent and color paste.
Preferably, the aliphatic isocyanate trimer is HDI trimer, and the solvent is butanone.
Preferably, the working slurry comprises 100 parts by weight of the 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 purpose, the invention provides the following technical scheme: the heat transfer film is prepared by coating the working slurry on a substrate, and drying the film.
Preferably, the thermal transfer film is prepared by applying the working slurry to the substrate by means of screen printing, and drying the formed film.
Preferably, the substrate is an OPP film.
More preferably, the working slurry is coated on the OPP film in an amount of 20 to 30g/m2。
Has the advantages that:
the polyurethane resin for thermal transfer printing has good thermal bonding performance in a heating film forming state, and realizes good adhesion with base cloth; after cooling, the product can be quickly crystallized to form a film, and after being peeled and separated from the OPP film, the surface is smooth and is anti-hot sticking.
The polyurethane resin for thermal transfer printing of the present invention can satisfy the requirements of a new thermal transfer printing process (an OPP film roller → a screen roller printing surface coated with polyurethane → an oven 1 for film formation and drying → a hot press roller for hot pressing and woven suede or cotton-like suede bonding → cooling → (product) from the OPP film, i.e., peeling and then winding).
The polyurethane resin for thermal transfer printing can be coated on an OPP film, transferred to woven suede or cotton-like suede through a heating transfer printing method, used for manufacturing technical cloth and further used for manufacturing technical cloth sofas.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention provides a polyurethane resin for thermal transfer printing, aiming at the problem that the existing polyurethane resin can not meet the requirements of a new thermal transfer printing process (OPP film roller → screen roller printing surface coating polyurethane → oven 1 film forming drying → hot pressing roller hot pressing and woven suede or cotton-like suede attaching → cooling → (product) peeling from the OPP film and then rolling up) on the polyurethane resin, wherein the polyurethane resin for thermal transfer printing is prepared from the following raw materials: a polyester diol of poly adipic acid series, a polyester diol of poly phthalic acid series, diphenylmethane-4, 4' -diisocyanate and a solvent.
According to the technical scheme, the polyurethane resin for thermal transfer printing has excellent thermal adhesiveness due to the introduction of the poly phthalic acid polyester diol. When the hot-pressing roller is heated and bonded, the hot-bonding roller has better hot bonding performance in a heating state, and can be well and firmly bonded with the base cloth in a hot-pressing state; the introduction of the poly adipic acid polyester diol provides excellent crystallinity of polyurethane resin, can be quickly crystallized to form a film after cooling, and ensures the heat adhesion resistance of the surface after being separated from an OPP film. The purpose of the invention is realized through the synergistic action of the poly phthalic acid polyester dihydric alcohol and the poly adipic acid polyester dihydric alcohol.
In a preferred embodiment of the present invention, the mass ratio of the polyadipic acid-based polyester diol to the polyphthalate-based polyester diol is 3:7 to 1:1 (for example, 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 acid polyester diol is 2000, and the number average molecular weight of the polyphthalate polyester diol is 2000.
In a preferred embodiment of the 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 (for example, 13.0 parts, 16.0 parts, 19.0 parts, 21.0 parts, 23.0 parts, 25.0 parts or 27.0 parts) of a polyadipate polyester diol, 22.0 to 37.5 parts (for example, 22.0 parts, 26.0 parts, 30.0 parts, 34.0 parts or 37.5 parts) of a polyphthalate polyester diol, 5.5 to 6.7 parts (for example, 5.5 parts, 5.7 parts, 5.9 parts, 6.1 parts, 6.3 parts, 6.5 parts or 6.7 parts) of a diphenylmethane-4, 4' -diisocyanate and 40 to 50 parts (for example, 40 parts, 42 parts, 46 parts, 48 parts or 50 parts) of a solvent.
In a preferred embodiment of the present invention, the polyadipic acid polyester diol is polyadipic acid-1, 4-butanediol polyester diol, the polyphthalate polyester diol is polyphthalate-diethylene glycol polyester diol, and the solvent is N, N-dimethylformamide. Particularly, the poly phthalic acid-diethylene glycol polyester diol introduced in the invention has a rigid structure containing benzene rings, so that the polyurethane resin for thermal transfer printing can meet the requirements of hand feeling and hardness required by technical cloth sofa without additionally introducing a glycol chain extender as a hard chain segment. Compared with the prior art that a diol chain extender is conventionally used as a hard chain segment, the system has the characteristic of good initial viscosity after film forming, and a formed polyurethane layer still has good initial viscosity even after a solvent is volatilized and dried, namely, the polyurethane resin for thermal transfer printing can be thermally laminated under the condition that the solvent is basically dried when being laminated, and good adhesion can be realized. The invention has very important significance for meeting the requirement of a new thermal transfer printing process (OPP film roller → polyurethane coated on the printing surface of a screen roller → drying of a film formed in an oven 1 → hot pressing of the hot pressing roller and the bonding of woven suede or cotton-like suede → cooling → product peeling and then rolling from the OPP film), namely lack of secondary drying, and can still realize the aim of the invention, further ensure that the hot pressing roller has better thermal bonding performance in a heating state and realizes better and firmer bonding with a base fabric in a hot pressing state when in heating and bonding.
The invention also provides a preparation method of the polyurethane resin for thermal transfer printing, which comprises the following steps: firstly, putting the poly adipic acid polyester dihydric alcohol, the phthalic acid polyester dihydric alcohol and part of the solvent into a reaction kettle at room temperature, uniformly mixing, and then carrying out the second step of reaction.
And a second step of adding the diphenylmethane-4, 4' -diisocyanate to the mixture obtained in the first step in portions, adding the remaining solvent after the viscosity of the reaction system has a viscosity value of 150-250 pas (e.g., 150 pas, 180 pas, 210 pas, 230 pas or 250 pas) as measured at 50 ℃, and terminating the reaction when the viscosity of the reaction system has a viscosity value of 80-140 pas (e.g., 80 pas, 100 pas, 120 pas, 130 pas or 140 pas) as measured at 20 ℃.
In a preferred embodiment of the present invention, a method for preparing a polyurethane resin for thermal transfer printing includes the steps of: the second step is specifically, adding a first batch of the diphenylmethane-4, 4 '-diisocyanate to the mixture obtained in the first step, heating to 70-80 ℃ (e.g., 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃ or 80 ℃) to make the solid content of the reaction system be 55-62% (e.g., 55%, 57%, 59%, 60% or 62%), and the NCO/OH molar ratio be 0.80, reacting until no NCO remains, adding the remaining diphenylmethane-4, 4' -diisocyanate until the viscosity of the reaction system is 150-250 pas (e.g., 150-250 pas, 180-s, 210-s, 230-s or 250-pas) as measured at 50 ℃, adding the remaining solvent, and detecting the viscosity of the reaction system again to be 150-250-pas (e.g., 150-s, 210-s, 230-s or 250-s) as measured at 50 ℃..g., again, 180, 210, 230 or 250Pa · s). According to the invention, the diphenylmethane-4, 4 '-diisocyanate is added twice, and compared with the method of adding the diphenylmethane-4, 4' -diisocyanate into the reaction system at one time, the method is beneficial to realizing the regulation of the regularity of the molecular structure generated by the reaction and is convenient for the control of production operation.
The invention also provides working slurry which comprises the polyurethane resin for thermal transfer printing.
In a preferred embodiment of the invention, the working slurry 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 HDI trimer, and the solvent is butanone.
In a preferred embodiment of the invention, the working slurry comprises, by weight, 100 parts 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 aliphatic isocyanate trimer, 90 to 110 parts (for example, 90 parts, 95 parts, 100 parts, 105 parts or 110 parts) of a solvent and 5 parts of a color paste.
The invention also provides a heat transfer printing film, which is prepared by coating the heat transfer printing polyurethane resin or the working slurry on a base material, and drying the formed film.
In a preferred embodiment of the present invention, the thermal transfer film is prepared by applying the thermal transfer polyurethane resin or the working slurry to the substrate by means of screen printing, and drying the film.
In a preferred embodiment of the present invention, the substrate is an OPP film.
In the preferred embodiment of the invention, when the working slurry is coated on the OPP film, the sizing amount is 20-30g/m2(e.g., 20 g/m)2、22g/m2、24g/m2、26g/m2、28g/m2Or 30g/m2)。
For convenience of writing, English abbreviations are used for raw materials used in the following examples, wherein PE-6 is a poly-1, 4-butanediol polyester diol having a number average molecular weight of 2000; HDPOL-320D is a poly (phthalic acid) -diethylene glycol polyester diol having a number average molecular weight of 2000; PE-3320 is poly adipic acid neopentyl glycol ester diol which is synthesized by condensation polymerization of adipic acid and neopentyl glycol and has the number average molecular weight of 2000 respectively; MDI is diphenylmethane-4, 4' -diisocyanate; DMF is N, N-dimethylformamide; the HDI trimer is hexamethylene diisocyanate trimer.
Example 1:
the polyurethane resin for thermal transfer printing of the present example was prepared using 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 solid content (solid content is 55%) into a reaction kettle, and uniformly mixing;
step 2:
adding 44.5 parts of MDI into the mixture obtained by the step 1, heating to 70 ℃ for reaction, controlling the solid content to be 55 percent and NCO/OH to be 0.80; reacting until no NCO residue is detected;
then, 11.1 parts of the remaining diphenylmethane-4, 4' -diisocyanate was added to the reaction system, and after the viscosity of the reaction system was measured at 50 ℃ and the viscosity value was 200Pa · s, the remaining 100.1 parts of N, N-dimethylformamide was added thereto, and the reaction was terminated when the viscosity of the reaction system was measured at 20 ℃ and the viscosity value was 120Pa · s, whereby the polyurethane resin for thermal transfer printing of example 1 was obtained.
Example 2:
the polyurethane resin for thermal transfer printing of the present example was prepared using 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:
putting 222.5 parts of PE-6, 222.5 parts of HDPOL-320D and 400.5 parts of N, N-dimethylformamide calculated according to solid content (solid content is 55%) into a reaction kettle, and uniformly mixing;
step 2:
adding 44.5 parts of MDI into the mixture obtained by the step 1, heating to 80 ℃ for reaction, controlling the solid content to be 55 percent and NCO/OH to be 0.80; reacting until no NCO residue is detected;
then, 11.1 parts of the remaining diphenylmethane-4, 4' -diisocyanate was added to the reaction system, and after the viscosity of the reaction system was measured at 50 ℃ and the viscosity value was 250Pa · s, the remaining 100.1 parts of N, N-dimethylformamide was added thereto, and the reaction was terminated when the viscosity of the reaction system was measured at 20 ℃ and the viscosity value was 136Pa · s, whereby the polyurethane resin for thermal transfer printing of example 2 was obtained.
Example 3:
the polyurethane resin for thermal transfer of the present example was prepared using 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 preparation method of polyurethane resin comprises the following steps:
step 1:
putting 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%) into a reaction kettle, and uniformly mixing;
step 2:
adding 49 parts of MDI into the mixture obtained by the step 1, heating to 75 ℃ for reaction, controlling the solid content to be 60 percent and NCO/OH to be 0.80; reacting until no NCO residue is detected;
and adding 12.3 parts of the remaining diphenylmethane-4, 4' -diisocyanate to the reaction system, adding 91.8 parts of the remaining N, N-dimethylformamide after the viscosity of the reaction system reaches a viscosity value of 170 pas measured at 50 ℃, and terminating the reaction when the viscosity of the reaction system reaches a viscosity value of 88 pas measured at 20 ℃ to obtain the polyurethane resin for thermal transfer printing of example 3.
Example 4:
the polyurethane resin for thermal transfer of the present example was prepared using 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:
245 parts of PE-6, 245 parts of HDPOL-320D and 359.3 parts of N, N-dimethylformamide calculated according to the solid content (solid content is 60%) are put into a reaction kettle and mixed uniformly;
step 2:
adding 49 parts of MDI into the mixture obtained by the step 1, heating to 70 ℃ for reaction, controlling the solid content to be 60 percent and NCO/OH to be 0.80; reacting until no NCO residue is detected;
and adding 12.3 parts of the remaining diphenylmethane-4, 4' -diisocyanate to the reaction system, adding 91.8 parts of the remaining N, N-dimethylformamide after the viscosity of the reaction system is 220 pas when the viscosity is measured at 50 ℃, and terminating the reaction when the viscosity is 128 pas when the viscosity is measured at 20 ℃ to obtain the polyurethane resin for thermal transfer printing of the example 4.
Example 5:
the polyurethane resin for thermal transfer printing of the present example was prepared using 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:
160.5 parts of PE-6, 374.5 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:
adding 53.5 parts of MDI into the mixture obtained by the step 1, heating to 70 ℃ for reaction, controlling the solid content to be 62 percent and NCO/OH to be 0.80; reacting until no NCO residue is detected;
and adding 13.4 parts of the remaining diphenylmethane-4, 4' -diisocyanate to the reaction system, adding 40.5 parts of the remaining N, N-dimethylformamide after the viscosity of the reaction system is measured at 50 ℃ and has a viscosity value of 200 pas, and terminating the reaction when the viscosity of the reaction system is measured at 20 ℃ and has a viscosity value of 116 pas to obtain the polyurethane resin for thermal transfer printing of example 5.
Example 6:
the polyurethane resin for thermal transfer of the present example was prepared using 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 realized 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:
adding 53.5 parts of MDI into the mixture obtained by the step 1, heating to 70 ℃ for reaction, controlling the solid content to be 62 percent and NCO/OH to be 0.80; reacting until no NCO residue is detected;
and adding 13.4 parts of the remaining diphenylmethane-4, 4' -diisocyanate to the reaction system, adding 40.5 parts of the remaining N, N-dimethylformamide after the viscosity of the reaction system is 230 pas as measured at 50 ℃, and terminating the reaction when the viscosity of the reaction system is 108 pas as measured at 20 ℃ to obtain the 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 using 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 printing of comparative example 1 was realized 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 solid content are put into a reaction kettle and uniformly mixed;
step 2:
adding 53.5 parts of MDI into the mixture obtained by the step 1, heating to 70 ℃ for reaction, controlling the solid content to be 62 percent and NCO/OH to be 0.80; reacting until no NCO residue is detected;
and adding 13.4 parts of residual diphenylmethane-4, 4' -diisocyanate into the reaction system, adding 40.5 parts of residual N, N-dimethylformamide after the viscosity of the reaction system is measured to be 200 Pa.s at 50 ℃, and stopping the reaction when the viscosity of the reaction system is measured to be 116 Pa.s at 20 ℃ to obtain 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 using 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 printing of comparative example 2 was achieved by the following process:
a preparation method of polyurethane resin for thermal transfer printing comprises the following steps:
step 1:
putting 535 parts of HDPOL-320D and 360.7 parts of N, N-dimethylformamide calculated according to solid content into a reaction kettle, and uniformly mixing;
step 2:
adding 53.5 parts of MDI into the mixture obtained by the step 1, and reacting at the temperature of 70 ℃, wherein the solid content is controlled to be 62 percent, and the NCO/OH is 0.80; reacting until no NCO residue is detected;
and adding 13.4 parts of residual diphenylmethane-4, 4' -diisocyanate into the reaction system, adding 40.5 parts of residual N, N-dimethylformamide after the viscosity of the reaction system is measured at 50 ℃ and has a viscosity value of 200 Pa.s, and terminating the reaction when the viscosity of the reaction system is measured at 20 ℃ and has a viscosity value of 120 Pa.s, thus obtaining the polyurethane resin for thermal transfer printing of the 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 in accordance with 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 in accordance with example 5.
Comparative example 5
The polyurethane resin for thermal transfer printing of this comparative example was prepared using 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 printing 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 printing of comparative example 5 was achieved 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, 2.61 parts of EG (ethylene glycol) and 423 parts of N, N-dimethylformamide calculated according to the solid content (the solid content is 55%) are put into a reaction kettle and mixed uniformly;
step 2:
adding 54.4 parts of MDI into the mixture obtained by the step 1, heating to 80 ℃ for reaction, controlling the solid content to be 55 percent and NCO/OH to be 0.80; reacting until no NCO residue is detected;
and adding 13.6 parts of residual diphenylmethane-4, 4' -diisocyanate into the reaction system, adding 108 parts of residual N, N-dimethylformamide after the viscosity value of the reaction system measured at 50 ℃ is 250 Pa.s, and terminating the reaction when the viscosity value of the reaction system measured at 20 ℃ is 136 Pa.s to obtain the polyurethane resin for thermal transfer printing of the comparative example 5.
The polyurethane resins for thermal transfer of examples 1 to 6, which are designated as No. 1 to 6 resins, and the polyurethane resins for thermal transfer of comparative examples 1 to 5, which are designated as No. 7 to 11 resins, were diluted with 100 parts of butanone to obtain solutions having a viscosity of 500-1000CPS/25 ℃ respectively, and 5 parts of brown syrup was added to the diluted solutions, and an aliphatic isocyanate trimer (HDI trimer) in an amount of 0% to 2% based on the example or comparative example resins was added. The HDI trimer with no addition (i.e., 0%) was numbered A, the HDI trimer with 2% addition was numbered B, and the diluted solutions were numbered 1A working slurry, 1B working slurry … …, up to 11A working slurry, 11B working slurry.
Working slurry of 1A, 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 5B, 6A, 6B, 7A, 7B, 8A, 8B, 9A, 9B, 10A, 10B, 11A and 11B is added at the ratio of 20g/m2Sizing, coating on an OPP film by a screen roller printing mode, sizing by a new thermal transfer printing process (OPP film roller → polyurethane coating on the printing surface of the screen roller → drying of film formation by an oven 1 → hot pressing of hot pressing roller and woven suede or cotton-like suede bonding → cooling → (product) from the OPP film, namely peeling and rolling), and adopting the woven suede as a base cloth for bonding; the adhesion fastness of the resin layer to suede after separation from the OPP film, and the heat-resistant tackiness and surface smoothness of the leather-like were compared.
Wherein, the adhesion fastness test is that after the rolling is finished, a leather sample of 20cm multiplied by 20cm is taken, a transparent adhesive tape is stuck on the surface of the leather sample, and then the leather sample is torn off, and the staining condition of the adhesive tape is compared; the test of the heat resistance viscosity is that after the rolling is finished, a 20cm multiplied by 20cm leather sample is taken, folded in half and placed under two glass plates, the two glass plates are placed in an oven at 100 ℃, the glass plates bear a load of 3 kilograms, and after 2 hours, the folded leather sample surface layer can be smoothly separated or not, so that the difference of the heat resistance viscosity of the leather sample is evaluated. The results of the experiment are shown in table 10 below:
TABLE 10 Properties of leather samples treated with the polyurethane resins for thermal transfer of examples 1 to 6 and comparative examples 1 to 4
As can be seen from table 10:
1. examples 1-6 corresponding 1A, 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 5B, 6A, 6B working pastes, which can be used for sizing in a new thermal transfer process, have better adhesion fastness and hot tack resistance. Meanwhile, compared with A, the addition of HDI trimer can improve the adhesion fastness.
2. The working slurries 7A, 7B, 8A, 8B corresponding to comparative examples 1-2, when sized using a new thermal transfer process, suffer from poor adhesion and are therefore not suitable for use in the new thermal transfer process. Although the addition of HDI trimer in B improves the adhesion strength to a suitable extent, it does not alter the result that it cannot be applied to new sizing for thermal transfer printing processes.
3. Comparative examples 3, 9A and 9B, respectively, showed improved adhesion due to the use of excessive HDPOL-320D, but had poor hot tack resistance. Comparative example 4, 10A and 10B, respectively, showed an increase in hot tack resistance due to the excessive use of PE-6. However, since both are not in the optimum range, the technical solutions of comparative examples 3 and 4 fail to satisfy the requirements of the new thermal transfer process.
4. 11A and 11B corresponding to comparative example 5 have the defect of poor adhesion when the new thermal transfer printing process is used for sizing, and cannot meet the requirements of the new thermal transfer printing process.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement 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 polyester diol of poly adipic acid series, a polyester diol of poly phthalic acid series, diphenylmethane-4, 4' -diisocyanate and a solvent.
2. The polyurethane resin for thermal transfer according to claim 1, wherein the mass ratio of the polyadipic acid-based polyester diol to the polyphthalate-based polyester diol is from 3:7 to 1: 1;
preferably, the number average molecular weight of the polyadipate polyester diol is 2000, and the number average molecular weight of the polyphthalate polyester diol is 2000.
3. The polyurethane resin for thermal transfer according to claim 1, which is prepared from raw materials comprising, in parts by weight: 13.0-27.0 parts of poly adipic acid polyester dihydric alcohol, 22.0-37.5 parts of poly phthalic acid polyester dihydric alcohol, 5.5-6.7 parts of diphenylmethane-4, 4' -diisocyanate and 40-50 parts of solvent;
preferably, the polyadipic acid polyester diol is polyadipic acid-1, 4-butanediol polyester diol, the polyphthalate polyester diol is polyphthalate-diethylene glycol polyester diol, and the solvent is N, N-dimethylformamide.
4. The method of producing the 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 dihydric alcohol, the poly phthalic acid polyester dihydric alcohol and part of the solvent into a reaction kettle, uniformly mixing, and then carrying out a second step of 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 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 detected again to be 80-140 Pa.s.
5. The method of claim 4, wherein the second step comprises adding a first amount of the diphenylmethane-4, 4 '-diisocyanate to the mixture obtained in the first step, heating to 70-80 ℃, allowing the reaction system to have a solid content of 55-62% and an NCO/OH molar ratio of 0.80, reacting until no NCO residue is detected, adding the remaining diphenylmethane-4, 4' -diisocyanate, adding the remaining solvent after the viscosity of the reaction system is 250 Pa.s, measured at 50 ℃, and stopping the reaction when the viscosity of the reaction system is 80-140 Pa.s, measured at 20 ℃.
6. A working slurry, characterized in that it comprises the polyurethane resin for thermal transfer according to any one of claims 1 to 3;
preferably, the working slurry also comprises aliphatic isocyanate tripolymer, 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 aliphatic isocyanate trimer, 90-110 parts by weight of a solvent and 5 parts by weight of a color paste.
9. A thermal transfer film, which is prepared by applying the working slurry according to any one of claims 6 to 8 to a substrate, and drying the applied film.
10. The thermal transfer film according to claim 9, wherein the thermal transfer film is prepared by applying the working slurry according to any one of claims 6 to 8 to the substrate by means of screen printing, and drying the formed film;
preferably, the substrate is an OPP film;
more preferably, the working slurry is coated on the OPP film in an amount of 20 to 30g/m2。
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