CN115322328B - Preparation method of epoxy modified polyurethane acrylate capable of being rapidly cured with low energy - Google Patents
Preparation method of epoxy modified polyurethane acrylate capable of being rapidly cured with low energy Download PDFInfo
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- CN115322328B CN115322328B CN202210999036.XA CN202210999036A CN115322328B CN 115322328 B CN115322328 B CN 115322328B CN 202210999036 A CN202210999036 A CN 202210999036A CN 115322328 B CN115322328 B CN 115322328B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
- C08G18/678—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
Abstract
The invention discloses a preparation method of epoxy modified polyurethane acrylic ester with low energy and rapid solidification, which comprises the following steps: 1) Preparing an epoxy compound containing hydroxyl groups from p-diethylaminobenzoic acid and the epoxy compound; 2) And reacting the diethylaminobenzoic acid and the glycidyl acrylate for a certain time under the action of a catalyst and a polymerization inhibitor, adding diisocyanate to continue to react for a certain time, and then adding an epoxy compound containing hydroxyl to react to obtain the low-energy fast-curing epoxy modified polyurethane acrylate. According to the invention, the epoxy modified polyurethane acrylate has a tertiary amine structure of 4-6 p-diethylaminobenzene on one molecule in a chemical modification mode, so that the oxygen sensitivity of the curing process is reduced, the curing speed is improved, the functionality is 2-3, the curing shrinkage and stress are small, and the epoxy modified polyurethane acrylate is particularly suitable for the fields of curing application (such as UV nail polish) which can only use low energy or the fields of curing which have large purity fluctuation of nitrogen shielding gas and need rapid curing.
Description
Technical Field
The invention belongs to the field of ultraviolet light curing, and particularly relates to a preparation method of epoxy modified polyurethane acrylate capable of being quickly cured with low energy.
Background
Most of the photo-curing processes of the ultraviolet light curing materials are carried out in an air environment, and the main application is thin coating materials with extremely large surface/volume ratio such as paint, ink and the like, so that the situation that the bottom layer of the coating is cured and the surface is not cured and sticky is often caused by oxygen polymerization inhibition, and particularly in a colored system, the phenomenon of oxygen polymerization inhibition is more obvious due to the competitive absorption of pigment or dye to ultraviolet light. Oxygen inhibition can eventually lead to the appearance of a large number of hydroxyl, carbonyl, peroxy and other oxidative structures on the surface layer of the coating, thereby affecting the long-term stability of the coating and possibly even affecting the hardness, glossiness, solvent resistance, scratch resistance and other properties of the cured paint film. This is particularly the case in UV-LED curing systems, since the UV-LED emits UV light at wavelengths of 390 nm,385nm and 405nm, and there is a lack of UV-C short wave UV light (200-300 nm) with a great influence of surface dryness.
Prepolymers such as polyurethane acrylic ester, epoxy acrylic ester, polyester acrylic ester, polyether acrylic ester and the like prepared by the conventional process have the problem of oxygen polymerization inhibition, and the surface solidification and drying are difficult to realize under low energy.
In order to overcome the influence of oxygen polymerization inhibition and improve the surface curing effect, the traditional method comprises the steps of preparing multifunctional UV resin, increasing the initiator amount, increasing the radiation dose, protecting nitrogen, coating a film, adding substances capable of providing active hydrogen and the like. However, in the preparation of multifunctional UV resins in practical applications, high-functional hydroxyl acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate is often used, and the synthesized UV resin generally has very large curing shrinkage, very large heat release in the curing process, and the problem that products with large curing stress are easy to curl; increasing the initiator dosage causes cost rise, has limited effect, and the residual initiator affects the subsequent aging performance; increasing the radiation dose causes the increase of power consumption and equipment cost, and the large radiation dose is unfavorable for ageing resistance of the material; nitrogen protection can only be achieved by specific equipment, and the industry often encounters the phenomenon that the purity of nitrogen is insufficient to limit the curing speed; the coating construction difficulty is high, bubbles are easy to form, and the surface is uneven; the active hydrogen substances are mainly amines and mercapto compounds, the smell of the amines and the mercapto compounds is large, the amines are easy to yellow, and the mercapto compounds are easy to Michael addition with double bonds after being directly added into the formula, so that the system is unstable in storage. In colored systems (such as ink, paint and the like), because of pigment and filler, dispersing agents are needed, and most of the dispersing agents are polymers containing carboxyl groups or amino groups, active amine is easy to react with the dispersing agents when added, so that the dispersing effect of the pigment is poor, and even sedimentation, flocculation and the like are caused.
Disclosure of Invention
The invention aims to provide the epoxy modified polyurethane acrylate which is low in energy and fast in curing and meets the application requirements. According to the invention, the epoxy compound containing hydroxyl is obtained by reacting the diethylaminobenzoic acid with the epoxy compound, and the hydroxyl acrylic ester obtained by reacting the diethylaminobenzoic acid with the glycidyl acrylate is reacted with isocyanate to obtain the epoxy modified polyurethane acrylic ester, wherein one molecule of the epoxy modified polyurethane acrylic ester is provided with 4-6 tertiary amine structures of the diethylaminobenzene, so that the oxygen sensitivity of the curing process is reduced, the oxygen sensitivity is reduced, the curing speed is improved, the functionality of the obtained epoxy modified polyurethane acrylic ester is 2-3 functions, the curing shrinkage and stress are small, and the epoxy modified polyurethane acrylic ester is particularly suitable for the fields of curing application (such as UV (ultraviolet) nail polish) or the fields of which have low purity of nitrogen shielding gas and need rapid curing.
The invention adopts the technical proposal for solving the problems that:
a preparation method of epoxy modified polyurethane acrylate with low energy and quick curing comprises the following steps:
1) Adding a mol of p-diethylaminobenzoic acid and b mol of epoxy compound with the functionality f into a reactor with mechanical stirring, then adding p-dimethylaminopyridine serving as a catalyst accounting for 0.01-0.5% of the total mass of all raw materials in the step, heating to 80-120 ℃, and reacting for 2-8 hours at a temperature maintaining condition to obtain the epoxy compound containing hydroxyl groups for later use;
2) Adding c mol of p-diethylaminobenzoic acid and d mol of glycidyl acrylate into a reactor with mechanical stirring, then adding catalyst p-dimethylaminopyridine accounting for 0.01-0.5% of the total mass of all raw materials in the step and polymerization inhibitor p-hydroxyanisole accounting for 0.01-0.5% of the total mass of all raw materials in the step, heating to 60-100 ℃, and reacting for 4-12 hours at a temperature of 60-100 ℃ in a heat preservation way (at the moment, obtaining hydroxyacrylate);
3) Reducing the temperature of the reaction system obtained in the step 2) to below 40 ℃, adding e mol of diisocyanate, then adding the catalyst dibutyltin dilaurate accounting for 0.01-0.3% of the mass of the materials added in the step and the polymerization inhibitor para-hydroxyanisole accounting for 0.01-0.5% of the mass of the materials added in the step, heating to 40-60 ℃ and carrying out heat preservation reaction for 1-4 hours (at the moment, obtaining a semi-adduct of hydroxyacrylate and isocyanate);
4) Adding g mol of the epoxy compound containing hydroxyl obtained in the first step into the reaction system obtained in the step 3), adding the catalyst dibutyltin dilaurate accounting for 0.01-0.3% of the mass of the materials added in the step, adding the polymerization inhibitor p-hydroxyanisole accounting for 0.01-0.5% of the mass of the materials added in the step, and heating to 70-80 ℃ for heat preservation reaction for 2-4 hours to obtain the low-energy quick-curing epoxy modified polyurethane acrylate.
According to the synthetic viscosity, the reactive diluent accounting for 0-30% of the total mass of the materials in the corresponding steps can be added in any step, so that the viscosity of the product is reduced, and the discharging is convenient.
In the preparation method, a is b=f 1, c is d:e=1:1:1, and g is c= (1/f) 1.
In the above preparation method, the epoxy resin with the functionality F comprises, but is not limited to, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, 4' -biphenol diglycidyl ether, resorcinol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether and the like, which are mixed according to any proportion. Wherein f=2-3.
In the above preparation method, the diisocyanate includes, but is not limited to, one or two of isophorone diisocyanate, 2,4 toluene diisocyanate and the like in any proportion.
Suitable examples of reactive diluents in the above preparation include, but are not limited to, isobornyl acrylate, 1,6 hexanediol diacrylate, dipropylene glycol diacrylate, tripalonic acid diacrylate, trimethylolpropane triacrylate, phenyl ethoxy acrylate, lauryl acrylate, and the like, in any ratio.
The epoxy modified polyurethane acrylate capable of being quickly cured with low energy has the characteristics of low odor, high curing speed, good toughness and the like. Compared with the prior art, the invention has the beneficial effects that:
firstly, the epoxy modified polyurethane acrylic ester with low energy and rapid curing can be used as a main component or an auxiliary agent adding system to be used as a hydrogen donor to be matched with a hydrogen-abstraction type photoinitiator, so that the curing speed is improved.
Secondly, the epoxy modified polyurethane acrylic ester capable of being quickly cured with low energy has very high curing speed, can reduce the dosage of a photoinitiator or the dosage of ultraviolet radiation, and realizes the reduction of cost.
Thirdly, the epoxy modified polyurethane acrylate with low energy and rapid curing has low sensitivity to oxygen polymerization inhibition, can be used in the fields with low energy curing or large purity fluctuation of nitrogen protection gas but rapid curing, and improves the process adaptability of products.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the invention further, but are not to be construed as limiting the invention.
Some of the specific raw materials used in the following examples are shown in Table 1.
TABLE 1
Example 1
A preparation method of epoxy modified polyurethane acrylate with low energy and quick curing comprises the following specific steps:
1) 386.48g (2 mol) of p-diethylaminobenzoic acid and 666.66g (1 mol) of polypropylene glycol diglycidyl ether with the functionality of 2 (the epoxy value is 0.3eq/100 g) are added into a reactor with mechanical stirring, 2g of catalyst p-dimethylaminopyridine is then added, the temperature is raised to 100-105 ℃ for heat preservation reaction for 4 hours, and a hydroxyl-containing epoxy compound with the theoretical functionality of 2 and the theoretical molecular weight of 1055.14 is obtained for standby;
2) 193.24g (1 mol) of p-diethylaminobenzoic acid and 128.13g (1 mol) of glycidyl acrylate are added into a reactor with mechanical stirring, then 0.65g of catalyst p-dimethylaminopyridine and 0.35g of polymerization inhibitor p-hydroxyanisole are added, the temperature is raised to 80-85 ℃ and the temperature is kept for reaction for 8 hours;
the temperature of the reactor is reduced to below 40 ℃, 174.16g (1 mol) of 2,4 toluene diisocyanate is added, then 0.32g of catalyst dibutyltin dilaurate and 0.1g of polymerization inhibitor para-hydroxyanisole are added, the temperature is raised to 50-55 ℃ for heat preservation reaction for 3 hours;
adding 527.57g (0.5 mol) of the hydroxyl-containing epoxy compound obtained in the first step into the reactor, adding 0.3g of dibutyltin dilaurate serving as a catalyst, 1g of p-hydroxyanisole serving as a polymerization inhibitor and 0.05g of o-methyl hydroquinone, heating to 70-75 ℃, and reacting for 4 hours at a temperature of between 70 and 75 ℃ to obtain the low-energy quick-curing epoxy modified polyurethane acrylate E-PUA-1.
Example 2
A preparation method of epoxy modified polyurethane acrylate with low energy and quick curing comprises the following specific steps:
1) 579.72g (3 mol) of p-diethylaminobenzoic acid and 444.17g (1 mol) of trimethylolpropane triglycidyl ether with a functionality of 3 (epoxy value 0.68eq/100 g) are added into a reactor with mechanical stirring, 3g of catalyst p-dimethylaminopyridine is then added, the temperature is raised to 105-110 ℃ and the reaction is carried out for 3 hours, so that an epoxy compound containing hydroxyl groups with a theoretical functionality of 3 and a theoretical molecular weight of 1026.89 is obtained for later use.
2) 193.24 (1 mol) of p-diethylaminobenzoic acid and 128.13 (1 mol) of glycidyl acrylate are added into a reactor with mechanical stirring, then 1g of catalyst p-dimethylaminopyridine and 0.3g of polymerization inhibitor p-hydroxyanisole are added, and the temperature is raised to 80-85 ℃ for thermal insulation reaction for 8 hours;
the temperature of the reactor is reduced to below 40 ℃, 174.16g (1 mol) of 2,4 toluene diisocyanate is added, then 0.25g of catalyst dibutyltin dilaurate and 0.1g of polymerization inhibitor para-hydroxyanisole are added, the temperature is raised to 45-50 ℃ and the temperature is kept for reaction for 3 hours;
342.30g (1/3 mol) of the hydroxyl-containing epoxy compound obtained in the first step and 100g of 1, 6-hexanediol diacrylate are continuously added into the reactor, then 0.8g of dibutyltin dilaurate serving as a catalyst, 0.75g of p-hydroxyanisole serving as a polymerization inhibitor and 0.08g of o-methyl hydroquinone are added, the temperature is raised to 80-85 ℃ and the temperature is kept for 3 hours, and the low-energy quick-curing epoxy modified polyurethane acrylate E-PUA-2 is obtained.
Example 3
A preparation method of epoxy modified polyurethane acrylate with low energy and quick curing comprises the following specific steps:
1) 386.48g (2 mol) of p-diethylaminobenzoic acid and 340g (1 mol) of bisphenol F epoxy resin with the functionality of 2 (epoxy value of 0.588eq/100 g) are added into a reactor with mechanical stirring, then 1.2g of catalyst p-dimethylaminopyridine is added, the temperature is raised to 110-115 ℃ for heat preservation reaction for 3 hours, and an epoxy compound containing hydroxyl is obtained, wherein the theoretical functionality is 2, the theoretical molecular weight is 727.68 for standby;
2) 193.24 (1 mol) of p-diethylaminobenzoic acid and 128.13 (1 mol) of glycidyl acrylate are added into a reactor with mechanical stirring, then 0.8g of catalyst p-dimethylaminopyridine and 0.35g of polymerization inhibitor p-hydroxyanisole are added, and the temperature is raised to 85-90 ℃ for thermal insulation reaction for 6 hours;
the temperature of the reactor is reduced to below 40 ℃, 222.29g (1 mol) of isophorone diisocyanate is added, then 0.4g of catalyst dibutyltin dilaurate and 0.15g of polymerization inhibitor para-hydroxyanisole are added, the temperature is raised to 50-55 ℃ for heat preservation reaction for 3 hours;
363.84g (0.5 mol) of the hydroxyl-containing epoxy compound obtained in the first step and 150g of dipropylene glycol diacrylate are continuously added into the reactor, then 0.9g of dibutyltin dilaurate serving as a catalyst, 0.88g of p-hydroxyanisole serving as a polymerization inhibitor and 0.055g of o-methyl hydroquinone are added, the temperature is raised to 75-80 ℃ and the temperature is kept for 4 hours, and the low-energy quick-curing epoxy modified polyurethane acrylate E-PUA-3 is obtained.
Performance test 1
The low energy fast curing epoxy modified urethane acrylates E-PUA-1, E-PUA-2, E-PUA-3 prepared in examples 1 to 3 were mixed with photoinitiators, respectively, and their curing speeds were tested as shown in Table 2. Wherein, the reactive amine P113, the epoxy acrylate CN104 NS and the common polyurethane acrylate CN966H90NS are used as the control.
Table 2: typical value Performance comparison of examples 1-3
The film thickness of the injection (1) in the air is 200+/-20 microns, the dominant wavelength is 365nm, and the irradiation intensity is 100mW/cm 2 The metal halide lamp is irradiated, and no fingerprint is touched by a finger on the surface to be regarded as the surface dryness.
As can be seen from Table 2, the low energy fast curing epoxy modified urethane acrylates E-PUA-1, E-PUA-2 and E-PUA-3 of the present invention have significantly faster curing rates than the conventional reactive amines and the conventional urethane acrylates and epoxy acrylates, at a minimum of 0.2J/cm 2 The surface dries under the radiation energy. As can be seen from comparison of the numbers 6 to 8 in Table 1: 10% of the epoxy modified polyurethane acrylate which is quickly cured with low energy is added into common polyurethane acrylate and epoxy acrylate, and can be cured under lower radiation dose under the condition of reducing the dosage of the photoinitiator 1173.
Performance test 2
The low energy fast curing epoxy modified urethane acrylates E-PUA-1, E-PUA-2, E-PUA-3 prepared in examples 1 to 3 were used as auxiliaries for UV resins (for example urethane acrylate CN966H90 NS) respectively in combination with a hydrogen abstraction type photoinitiator (for example benzophenone) and the curing speeds were tested as shown in Table 3. Wherein, active amine P113 is used as a control; and CN966H90NS was used in combination with the photoinitiator benzophenone as a blank.
Table 3: comparison of formulation Properties of examples 1-3
| Sequence number | Resin name | Time of surface dry (1) |
| 1 | E-PUA-1: CN966H90 NS: photoinitiator benzophenone=5:95:2 | 12s |
| 2 | E-PUA-2: CN966H90 NS: photoinitiator benzophenone=5:95:2 | 10s |
| 3 | E-PUA-3: CN966H90 NS: photoinitiator benzophenone=5:95:2 | 11s |
| 4 | Reactive amine P115: CN966H90 NS: photoinitiator benzophenone=5:95:2 | 80s |
| 5 | CN966H90 ns:photoinitiator benzophenone=100:2 | No surface drying for 200 seconds |
The film thickness of the injection (1) in the air is 200+/-20 microns, the dominant wavelength is 365nm, and the irradiation intensity is 100mW/cm 2 Gold of (2)Belonging to the field of illumination under a halogenation lamp,
the finger touching the surface without fingerprint is regarded as the surface dryness.
As shown in Table 3, the low-energy fast-curing epoxy modified polyurethane acrylic ester E-PUA-1, E-PUA-2 and E-PUA-3 are added into the formula as auxiliary agents to be used in combination with hydrogen-abstraction type photoinitiator benzophenone, so that the surface drying speed can be remarkably improved, and the effect is superior to that of active amine P115 with equal quality.
Performance test 3
The low energy fast curing epoxy modified urethane acrylates E-PUA-1, E-PUA-2, E-PUA-3 prepared in examples 1-3 were used as adjuvants for UV resins (urethane acrylate CN966H90NS is taken as an example) respectively in combination with photoinitiators, and the curing speeds under nitrogen protection were tested as shown in Table 4.
Table 4: comparison of formulation Properties of examples 1-3
The injection (1) is coated on a PET film, the thickness is 100+/-20 micrometers, and the PET film is cured by using a conveyor belt type ultraviolet curing machine, the power of an ultraviolet lamp is 1000W, and the irradiation distance is 50cm.
As can be seen from Table 4, the conventional urethane acrylate CN966H90NS can achieve a curing speed of 10 m/min under the protection of high purity nitrogen, but the curing speed can only reach 2 m/min when the purity of nitrogen is reduced to 95%. By adding 5% of the low-energy fast-curing epoxy modified polyurethane acrylate E-PUA-1, E-PUA-2 or E-PUA-3, the curing speed of 10 m/min can still be realized under the condition of 95% of nitrogen purity, and the process adaptability of the product is effectively improved.
The foregoing description of the invention is merely a preferred embodiment of the invention, and it should be noted that modifications and changes can be made by those skilled in the art without departing from the inventive concept, which fall within the scope of the invention.
Claims (5)
1. The preparation method of the epoxy modified polyurethane acrylate with low energy and quick curing is characterized by comprising the following steps:
1) Mixing c mol of p-diethylaminobenzoic acid and d mol of glycidyl acrylate, adding a catalyst p-dimethylaminopyridine and a polymerization inhibitor p-hydroxyanisole, heating to 60-100 ℃, and reacting for 4-12 hours at a temperature of between 60 and 100 ℃;
2) After the temperature of the reaction system in the step 1) is reduced to below 40 ℃, adding e mol of diisocyanate, then adding a catalyst dibutyl tin dilaurate and a polymerization inhibitor p-hydroxyanisole, heating to 40-60 ℃, and carrying out heat preservation reaction for 1-4 hours; wherein, c: d: e=1:1:1;
3) Adding g mol of hydroxyl-containing compound into the reaction system obtained in the step 2), then adding catalyst dibutyl tin dilaurate, polymerization inhibitor p-hydroxyanisole and polymerization inhibitor o-methyl hydroquinone, heating to 70-80 ℃ for heat preservation reaction for 2-4 hours, and obtaining the epoxy modified polyurethane acrylate with low energy and rapid solidification;
the preparation method of the hydroxyl-containing compound comprises the following steps: adding a mol of p-diethylaminobenzoic acid and b mol of epoxy compound with the functionality f into a reactor with mechanical stirring, then adding p-dimethylaminopyridine serving as a catalyst accounting for 0.01-0.5% of the total mass of all raw materials in the step, heating to 80-120 ℃, and reacting for 2-8 hours at a temperature maintaining condition to obtain the epoxy compound containing hydroxyl; wherein a: b=f: 1, g: c= (1/f): 1.
2. The method for preparing the low-energy fast-curing epoxy modified polyurethane acrylate according to claim 1, wherein the epoxy compound with the functionality of F comprises one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, 4' -biphenol diglycidyl ether, resorcinol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and glycerol triglycidyl ether according to any proportion.
3. The method for preparing the low-energy fast-curing epoxy modified polyurethane acrylate according to claim 1, wherein a reactive diluent accounting for 0-30% of the total mass of materials in the corresponding step is added in any step to adjust the viscosity.
4. The method for preparing the low-energy fast-curing epoxy modified polyurethane acrylate according to claim 3, wherein the reactive diluent comprises one or a mixture of several of isobornyl acrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripalonic acid diacrylate, trimethylolpropane triacrylate, phenyl ethoxy acrylate and lauryl acrylate according to any proportion.
5. The method for preparing the low-energy fast-curing epoxy modified polyurethane acrylate according to claim 1, wherein the diisocyanate comprises one or a mixture of two of isophorone diisocyanate and toluene diisocyanate according to any proportion.
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