CN109666127B - Self-leveling light-cured polyurethane resin for synthetic leather and preparation method thereof - Google Patents
Self-leveling light-cured polyurethane resin for synthetic leather and preparation method thereof Download PDFInfo
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- CN109666127B CN109666127B CN201811479822.7A CN201811479822A CN109666127B CN 109666127 B CN109666127 B CN 109666127B CN 201811479822 A CN201811479822 A CN 201811479822A CN 109666127 B CN109666127 B CN 109666127B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/4808—Mixtures of two or more polyetherdiols
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a self-leveling light-cured polyurethane resin for synthetic leather and a preparation method thereof, wherein the self-leveling light-cured polyurethane resin for synthetic leather is prepared from the following raw materials: polyol, organosilicon modified polyether polyol, diisocyanate, a blocking agent, a common diluent and a low surface energy diluent. The invention can naturally wet the base material in a short time without adding a leveling assistant, and meets the requirement of resin leveling during fast curing by illumination; secondly, the self-leveling photocuring polyurethane resin for synthetic leather introduces the low-surface-energy diluent containing the long alkyl chain, is beneficial to wetting and leveling of the resin, avoids the problem of brittleness of the resin caused by the introduction of an acrylic monomer, and has good folding resistance at normal and low temperatures; thirdly, the self-leveling light-cured polyurethane resin for synthetic leather provided by the invention does not discharge solvent in the preparation and curing processes, and is an environment-friendly and energy-saving product.
Description
Technical Field
The invention relates to polyurethane resin and a preparation method thereof, in particular to self-leveling light-cured polyurethane resin for synthetic leather and a preparation method thereof.
Background
With the development of socioeconomic, consumers are continuously aroused when pursuing product quality. The synthetic leather industry consumes a large amount of harmful substances such as organic solvents and the like, and the environmental pollution is increasingly serious. Accordingly, the related art has invested much effort in developing environmentally friendly synthetic leather technologies for the future, and one of them is photocuring synthetic leather technologies.
The resin for the photocuring synthetic leather has no solvent emission in the curing process, low VOC content and environmental protection; in addition, the production efficiency is high, the curing and molding can be carried out within seconds or tens of seconds, high-temperature heating is not needed, and the energy consumption is low. Accordingly, there is a need for resins that have lower viscosity at room temperature, lower surface energy, and can wet and level in a short time. In addition, polyurethane resins for leather generally have good flexibility, and the introduction of a large amount of acrylic diluent monomer tends to make the resin brittle and needs to be dealt with reasonably.
Disclosure of Invention
The invention aims to provide a self-leveling light-cured polyurethane resin for synthetic leather and a preparation method thereof, so as to meet the application requirements of related fields.
The self-leveling light-cured polyurethane resin for the synthetic leather is prepared from the following raw materials:
polyol, organosilicon modified polyether polyol, diisocyanate, a blocking agent, a common diluent and a low surface energy diluent;
preferably, the resin also comprises a polymerization inhibitor, wherein the dosage of the polymerization inhibitor is 0.2-0.5% of the total weight of the resin;
the dosage of the organic silicon modified polyether glycol is 0.5 to 1.5 percent of the total weight of the resin;
the ratio of the total moles of diisocyanate to the total moles of polyol is 1.5-3: 1;
the ratio of the total moles of the blocking agent to the total moles of the diisocyanate is 0.9-1.5: 1;
the dosage of the common diluent and the low surface energy diluent is 10 to 25 percent of the total weight of the polyol, the organosilicon modified polyether polyol, the diisocyanate and the end-capping agent;
preferably, the polyol is selected from one or more of polypropylene oxide/ethylene oxide ether triol, polypropylene oxide ether triol, polytetrahydrofuran ether glycol, polypropylene oxide/ethylene oxide ether glycol, polycaprolactone glycol, poly neopentyl glycol adipate glycol and poly hexanediol adipate glycol, and the number average molecular weight of the polyol is 500-8000;
preferably, the organosilicon modified polyether polyol is selected from one of hydroxyl-terminated single-functionality organosilicon modified polyether, hydroxyl-terminated double-functionality organosilicon modified polyether, hydroxyl-terminated four-functionality organosilicon modified polyether and side hydroxyl-terminated double-functionality organosilicon modified polyether;
the hydroxyl-terminated monofunctional organosilicon modified polyether is purchased from Stokes high molecular polymer Co., Ltd, Guangzhou;
the hydroxyl-terminated difunctional silicone modified polyether is purchased from Stokes high molecular polymer Co., Ltd, Guangzhou;
the hydroxyl-terminated tetrafunctional silicone modified polyether is purchased from dow corning corporation;
the side hydroxyl difunctional silicone modified polyether is purchased from mays corporation;
preferably, the end-capping reagent is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
preferably, the common diluent is one or more selected from hydroxyethyl acrylate, hydroxypropyl acrylate, isooctyl acrylate, glycidyl methacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate and trimethylolpropane triacrylate;
preferably, the low surface energy diluent is selected from one or more of 3,3, 5-trimethylcyclohexyl acrylate, lauric acid acrylate, isodecyl acrylate, isotridecyl methacrylate and isobornyl acrylate;
preferably, the diisocyanate is selected from at least two of Toluene Diisocyanate (TDI), 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane 4, 4-diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), tetramethylxylylene diisocyanate (TMXDI)); preferably one or two of diphenylmethane diisocyanate, toluene diisocyanate and hexamethylene diisocyanate;
preferably, the polymerization inhibitor is selected from one or two of hydroquinone and p-methoxyphenol.
The preparation method of the self-leveling light-cured polyurethane resin for the synthetic leather comprises the following steps:
1) putting polyol and organic silicon modified polyether polyol into a reaction kettle, mixing, and uniformly stirring at 50-60 ℃;
2) putting diisocyanate into a reaction kettle in batches, enabling the reaction temperature to be 65-80 ℃, reacting for 2-8 hours under normal pressure, measuring the NCO content once every half hour after the system reaches a certain viscosity, putting a blocking agent and a polymerization inhibitor when the NCO content meets the theoretical requirement, stopping heating when the NCO content is zero, cooling to below 40 ℃, putting a diluent, and uniformly mixing to obtain the self-leveling light-cured polyurethane resin for the synthetic leather.
The invention has the following beneficial effects:
the self-leveling light-cured polyurethane resin for synthetic leather can naturally wet the base material in a short time without adding a leveling assistant, and meets the requirement of resin leveling during rapid curing by illumination; secondly, the self-leveling photocuring polyurethane resin for synthetic leather introduces the low-surface-energy diluent containing the long alkyl chain, is beneficial to wetting and leveling of the resin, avoids the problem of brittleness of the resin caused by the introduction of an acrylic monomer, and has good folding resistance at normal and low temperatures; thirdly, no solvent is discharged in the preparation and curing processes of the self-leveling light-cured polyurethane resin for synthetic leather, and the self-leveling light-cured polyurethane resin belongs to an environment-friendly and energy-saving product; is beneficial to the environmental protection transformation of the synthetic leather.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention. The starting materials used in the following examples are all commercially available.
Example 1
The raw materials and weights used in this example are shown in Table 1.
TABLE 1
| Name of raw materials | Weight (unit: gram) |
| Polypropylene oxide/ethylene oxide Ether triol (number average molecular weight 6000) | 630 |
| Polypropylene oxide Ether diol (number average molecular weight 2000) | 68 |
| Lateral hydroxyl two-functionality organosilicon modified polyether (number average molecular weight 1700) | 9 |
| Diphenylmethane diisocyanate | 49.4 |
| Toluene diisocyanate | 34.4 |
| Acrylic acid hydroxy ethyl ester | 68.8 |
| 1, 6-hexanediol diacrylate | 80 |
| Lauric acid acrylate | 100 |
| Hydroquinone | 3 |
The preparation steps of the self-leveling light-curing polyurethane resin for synthetic leather of the embodiment are as follows:
1) 630g of polypropylene oxide/ethylene oxide ether triol, 68g of polypropylene oxide ether glycol and 9g of side hydroxyl two-functional organic silicon modified polyether are put into a reaction kettle and are stirred uniformly at 50 ℃;
2) putting 49.4g of diphenylmethane diisocyanate and 34.4g of toluene diisocyanate into a reaction kettle in batches, strictly controlling the reaction temperature to be 75-80 ℃, sampling every half hour to determine the NCO content after reacting for 5 hours under normal pressure, putting 68.8g of capping agent hydroxyethyl acrylate and 3g of polymerization inhibitor hydroquinone when the NCO content is lower than 2.1%, continuing to react at 75-80 ℃, stopping heating when the NCO content is zero, cooling to below 40 ℃, putting 80g of 1, 6-hexanediol diacrylate and 100g of lauric acid acrylate, and uniformly mixing to obtain the self-leveling light-cured polyurethane resin for synthetic leather.
Mixing 100g of the obtained resin and 1.5g of photoinitiator Darocur-1173 by a dispersion machine, then coating about 0.2mm on release paper by blade coating, and curing by a UV curing machine; the obtained adhesive film has good leveling property.
The normal temperature folding endurance test method comprises the following steps: cutting 5 sample sheets from the prepared adhesive film by using a cutting mold (45 × 70mm), respectively installing the cut sample sheets on a normal-temperature (25 ℃) folding endurance testing machine (Taiwan high-speed rail, equipment model GT-7071-B) for testing according to set conditions, and recording folding endurance results according to test conditions.
The low-temperature folding endurance test method comprises the following steps: the prepared adhesive film is cut into 5 sample sheets by using a folding-resistant cutting mold (45 × 70mm), and the folding-resistant times are tested under the temperature condition (-20 ℃). And respectively mounting the cut sample wafers on a low-temperature folding endurance testing machine (Taiwan Honda, equipment model HT-8043) to test according to set conditions, and recording folding endurance results according to test conditions.
The results according to the normal temperature and low temperature test method were: the product is resistant to folding at normal temperature, and does not crack for 20 ten thousand times, and does not crack for 8 ten thousand times at minus 20 ℃.
Example 2
The raw materials and weights used in this example are shown in Table 2.
TABLE 2
| Name of raw materials | Weight (unit: gram) |
| Polypropylene oxide Ether diol (number average molecular weight 2000) | 690 |
| Lateral hydroxyl two-functionality organosilicon modified polyether (number average molecular weight 1700) | 9 |
| Toluene diisocyanate | 122 |
| Hydroxypropyl acrylate | 110 |
| 1, 6-hexanediol diacrylate | 30 |
| Glycidyl methacrylate | 30 |
| Isodecyl acrylate | 60 |
| Hydroquinone | 3 |
The preparation steps of the self-leveling light-curing polyurethane resin for synthetic leather of the embodiment are as follows:
1) 690g of polypropylene oxide ether glycol and 9g of side hydroxyl bifunctional organic silicon modified polyether are put into a reaction kettle and stirred at 55 ℃;
2) 122g of toluene diisocyanate is put into a reaction kettle in batches, the reaction temperature is strictly controlled to be 75-80 ℃, after the reaction is carried out for 4 hours under normal pressure, sampling is carried out every half hour to measure the NCO content, when the NCO content is lower than 3.6%, 110g of end-capping agent hydroxypropyl acrylate and 3g of polymerization inhibitor hydroquinone are put into the reaction kettle, the reaction is carried out at 75-80 ℃, when the NCO content is zero, heating is stopped, the reaction kettle is cooled to be lower than 40 ℃, 30g of 1, 6-hexanediol diacrylate, 30g of glycidyl methacrylate and 60g of isodecyl acrylate are put into the reaction kettle, and the self-leveling photocuring polyurethane resin for synthetic leather can be obtained after uniform mixing.
Mixing 100g of the obtained resin and 1.5g of photoinitiator Darocur-1173 by a dispersion machine, then coating about 0.2mm on release paper by blade coating, and curing by a UV curing machine; the obtained adhesive film has good leveling property, is folding-resistant at normal temperature, and does not crack for 15 ten thousand times, and does not crack for 4 ten thousand times at the temperature of minus 20 ℃.
Example 3
The raw materials and weights used in this example are shown in Table 3.
TABLE 3
| Name of raw materials | Weight (unit: gram) |
| Polyneopentyl glycol adipate diol (number average molecular weight 2000) | 150 |
| Polypropylene oxide Ether diol (number average molecular weight 2000) | 438 |
| Polypropylene oxide/ethylene oxide Ether diol (number average molecular weight 1000) | 100 |
| Lateral hydroxyl two-functionality organosilicon modified polyether (number average molecular weight 1700) | 10 |
| Diphenylmethane diisocyanate | 40 |
| Toluene diisocyanate | 111.4 |
| Acrylic acid hydroxy ethyl ester | 139.2 |
| Glycidyl methacrylate | 40 |
| Trimethylolpropane triacrylate | 30 |
| 3,3, 5-trimethylcyclohexyl acrylate | 80 |
| Hydroquinone | 3 |
The preparation steps of the self-leveling light-curing polyurethane resin for synthetic leather of the embodiment are as follows:
1) 150g of poly neopentyl glycol adipate glycol, 100g of polypropylene oxide/ethylene oxide ether glycol and 450g of polypropylene oxide ether glycol are put into a reaction kettle, 10g of side hydroxyl two-functional organic silicon modified polyether is put into the reaction kettle, and the mixture is stirred uniformly at 55 ℃;
2) putting 40g of diphenylmethane diisocyanate and 111.4.4g of toluene diisocyanate into a reaction kettle in batches, strictly controlling the reaction temperature to be 65-70 ℃, sampling every half hour to determine the NCO content after reacting for 3 hours under normal pressure, putting 139.2g of blocking agent hydroxyethyl acrylate and 3g of polymerization inhibitor hydroquinone after the NCO content is lower than 3.9, continuing to react at 75-80 ℃, stopping heating when the NCO content is zero, cooling to below 40 ℃, putting 30g of trimethylolpropane triacrylate, 40g of glycidyl methacrylate and 80g of 3,3, 5-trimethylcyclohexyl acrylate, and uniformly mixing to obtain the self-leveling photocuring polyurethane resin for synthetic leather.
Mixing 100g of the obtained resin and 1.5g of photoinitiator Darocur-1173 by a dispersion machine, then coating about 0.2mm on release paper by blade coating, and curing by a UV curing machine; the obtained adhesive film has good leveling property, is folding-resistant at normal temperature, and does not crack for 15 ten thousand times, and does not crack for 4 ten thousand times at the temperature of minus 20 ℃.
Example 4
The raw materials and weights used in this example are given in Table 4 below.
TABLE 4
| Name of raw materials | Weight (unit: gram) |
| Poly (methyl propylene glycol adipate) glycol (number average molecular weight 1800) | 200 |
| Polypropylene oxide/ethylene oxide Ether diol (number average molecular weight 2000) | 443 |
| Hydroxyl-terminated two-functionality organosilicon modified polyether (number average molecular weight 3550) | 12 |
| Diphenylmethane diisocyanate | 126 |
| Acrylic acid hydroxy ethyl ester | 58 |
| Neopentyl glycol diacrylate | 100 |
| Isotridecyl methacrylate | 80 |
| Hydroquinone | 3 |
The preparation steps of the self-leveling light-curing polyurethane resin for synthetic leather of the embodiment are as follows:
1) putting 200g of poly (methyl propylene glycol adipate) glycol, 443g of poly (propylene oxide)/ethylene oxide ether glycol and 12g of terminal hydroxyl two-functional organic silicon modified polyether into a reaction kettle, and uniformly stirring at 50-55 ℃;
2) 126g of diphenylmethane diisocyanate is put into a reaction kettle in batches, the reaction temperature is strictly controlled to be 65-70 ℃, after the reaction is carried out for 3 hours under normal pressure, the sample is taken every half hour to measure the NCO content, when the NCO content is lower than 1.8 percent, 58 g of end capping agent hydroxyethyl acrylate and 3g of polymerization inhibitor hydroquinone are put into the reaction kettle, the reaction is carried out at 75-80 ℃, when the NCO content is zero, the heating is stopped, the temperature is cooled to be lower than 40 ℃, 100g of neopentyl glycol diacrylate and 80g of isotridecyl methacrylate are put into the reaction kettle, and the mixture is uniformly mixed, so that the self-leveling light-cured polyurethane resin for synthetic leather can be obtained.
Mixing 100g of the obtained resin and 1.5g of photoinitiator Darocur-1173 by a dispersion machine, then coating about 0.2mm on release paper by blade coating, and curing by a UV curing machine; the obtained adhesive film has good leveling property, is folding-resistant at normal temperature, and does not crack for 18 ten thousand times, and does not crack for 4 ten thousand times at the temperature of minus 20 ℃.
Example 5
The raw materials and weights used in this example are shown in Table 5.
TABLE 5
| Name of raw materials | Weight (unit: gram) |
| Polypropylene oxide/ethylene oxide Ether triol (number average molecular weight 6000) | 630 |
| Polypropylene oxideEther diol (number average molecular weight 2000) | 68 |
| Hydroxyl-terminated two-functionality organosilicon modified polyether (number average molecular weight 3550) | 13 |
| Diphenylmethane diisocyanate | 49.4 |
| Toluene diisocyanate | 34.4 |
| Acrylic acid hydroxy ethyl ester | 68.8 |
| 1, 6-hexanediol diacrylate | 80 |
| Isobornyl acrylate | 100 |
| Hydroquinone | 3 |
The preparation steps of the self-leveling light-curing polyurethane resin for synthetic leather of the embodiment are as follows:
1) 630g of polypropylene oxide/ethylene oxide ether triol, 68g of polypropylene oxide ether glycol and 13g of hydroxyl-terminated two-functional organic silicon modified polyether are put into a reaction kettle and are uniformly stirred at 50-55 ℃;
2) putting 49.4g of diphenylmethane diisocyanate and 34.4g of toluene diisocyanate into a reaction kettle in batches, strictly controlling the reaction temperature to be 75-80 ℃, sampling every half hour to determine the NCO content after reacting for 5 hours under normal pressure, putting 68.8g of capping agent hydroxyethyl acrylate and 3g of polymerization inhibitor hydroquinone when the NCO content is lower than 2.1%, continuing to react at 75-80 ℃, stopping heating when the NCO content is zero, cooling to below 40 ℃, putting 80g of 1, 6-hexanediol diacrylate and 100g of isobornyl acrylate, and uniformly mixing to obtain the self-leveling light-cured polyurethane resin for synthetic leather.
Mixing 100g of the obtained resin and 1.5g of photoinitiator Darocur-1173 by a dispersion machine, then coating about 0.2mm on release paper by blade coating, and curing by a UV curing machine; the obtained adhesive film has good leveling property, is folding-resistant at normal temperature, and does not crack for 20 ten thousand times, and does not crack for 8 ten thousand times at the temperature of minus 20 ℃.
Example 6
The raw materials and weights used in this example are shown in Table 6.
TABLE 6
The preparation steps of the self-leveling light-curing polyurethane resin for synthetic leather of the embodiment are as follows:
1) putting 690g of polypropylene oxide ether glycol and 14g of terminal hydroxyl bifunctional organic silicon modified polyether into a reaction kettle, and stirring at 50-55 ℃;
2) 122g of toluene diisocyanate is put into a reaction kettle in batches, the reaction temperature is strictly controlled to be 75-80 ℃, after reaction for 4 hours under normal pressure, sampling is carried out every half hour to measure the NCO content, when the NCO content is lower than 3.6%, 110g of end-capping agent hydroxypropyl acrylate and 3g of polymerization inhibitor hydroquinone are put into the reaction kettle, the reaction is carried out at 75-80 ℃, when the NCO content is zero, heating is stopped, the reaction kettle is cooled to be lower than 40 ℃, 30g of 1, 6-hexanediol diacrylate, 30g of glycidyl methacrylate and 60g of lauric acid acrylate are put into the reaction kettle, and the self-leveling light-cured polyurethane resin for synthetic leather can be obtained after uniform mixing.
Mixing 100g of the obtained resin and 1.5g of photoinitiator Darocur-1173 by a dispersion machine, then coating about 0.2mm on release paper by blade coating, and curing by a UV curing machine; the obtained adhesive film has good leveling property, is folding-resistant at normal temperature, and does not crack for 15 ten thousand times, and does not crack for 4 ten thousand times at the temperature of minus 20 ℃.
Example 7
The raw materials and weights used in this example are shown in Table 7.
TABLE 7
The preparation steps of the self-leveling light-curing polyurethane resin for synthetic leather of the embodiment are as follows:
1) 150g of poly neopentyl glycol adipate glycol, 100g of polypropylene oxide/ethylene oxide ether glycol and 450g of polypropylene oxide ether glycol are put into a reaction kettle, 8g of terminal hydroxyl monofunctional organic silicon modified polyether is put into the reaction kettle, and the mixture is stirred uniformly at 53 ℃;
2) putting 40g of diphenylmethane diisocyanate and 111.4.4g of toluene diisocyanate into a reaction kettle in batches, strictly controlling the reaction temperature to be 65-70 ℃, sampling every half hour to determine the NCO content after reacting for 3 hours under normal pressure, putting 139.2g of blocking agent hydroxyethyl acrylate and 3g of polymerization inhibitor hydroquinone after the NCO content is lower than 3.9, continuing to react at 75-80 ℃, stopping heating when the NCO content is zero, cooling to below 40 ℃, putting 30g of trimethylolpropane triacrylate, 40g of glycidyl methacrylate and 80g of isodecyl acrylate, and uniformly mixing to obtain the self-leveling light-cured polyurethane resin for synthetic leather.
Mixing 100g of the obtained resin and 1.5g of photoinitiator Darocur-1173 by a dispersion machine, then coating about 0.2mm on release paper by blade coating, and curing by a UV curing machine; the obtained adhesive film has good leveling property, is folding-resistant at normal temperature, and does not crack for 15 ten thousand times, and does not crack for 4 ten thousand times at the temperature of minus 20 ℃.
Example 8
The raw materials and weights used in this example are shown in Table 8 below.
TABLE 8
| Name of raw materials | Weight (unit: gram) |
| Poly (methyl propylene glycol adipate) glycol (number average molecular weight 1800) | 200 |
| Polypropylene oxide/ethylene oxide Ether diol (number average molecular weight 2000) | 443 |
| Hydroxyl terminated monofunctional silicone modified polyether (number average molecular weight 1300) | 7 |
| Diphenylmethane diisocyanate | 126 |
| Acrylic acid hydroxy ethyl ester | 58 |
| Neopentyl glycol diacrylate | 100 |
| 3,3, 5-trimethylcyclohexyl acrylate | 80 |
| Hydroquinone | 3 |
The preparation steps of the self-leveling light-curing polyurethane resin for synthetic leather of the embodiment are as follows:
1) putting 200g of poly (methyl propylene glycol adipate) glycol, 443g of poly (propylene oxide)/ethylene oxide ether glycol and 7g of terminal hydroxyl monofunctional organic silicon modified polyether into a reaction kettle, and uniformly stirring at 50-55 ℃;
2) 126g of diphenylmethane diisocyanate is put into a reaction kettle in batches, the reaction temperature is strictly controlled to be 65-70 ℃, after the reaction is carried out for 3 hours under normal pressure, the sample is taken every half hour to measure the NCO content, when the NCO content is lower than 1.8 percent, 58 g of end capping agent hydroxyethyl acrylate and 3g of polymerization inhibitor hydroquinone are put into the reaction kettle, the reaction is carried out at 75-80 ℃, when the NCO content is zero, the heating is stopped, the reaction kettle is cooled to be lower than 40 ℃, 100g of neopentyl glycol diacrylate and 80g of 3,3, 5-trimethylcyclohexyl acrylate are put into the reaction kettle, and the mixture is uniformly mixed, so that the self-leveling light-cured polyurethane resin for synthetic leather can be obtained.
Mixing 100g of the obtained resin and 1.5g of photoinitiator Darocur-1173 by a dispersion machine, then coating about 0.2mm on release paper by blade coating, and curing by a UV curing machine; the obtained adhesive film has good leveling property, is folding-resistant at normal temperature, and does not crack for 18 ten thousand times, and does not crack for 4 ten thousand times at the temperature of minus 20 ℃.
Example 9
The raw materials and weights used in this example are shown in Table 9.
TABLE 9
| Name of raw materials | Weight (unit: gram) |
| Polypropylene oxide/ethylene oxide Ether triol (number average molecular weight 6000) | 630 |
| Gathering ringOxypropane Ether diol (number average molecular weight 2000) | 68 |
| Hydroxyl-terminated tetrafunctional silicone modified polyether (number average molecular weight 6000) | 5 |
| Diphenylmethane diisocyanate | 49.4 |
| Toluene diisocyanate | 34.4 |
| Acrylic acid hydroxy ethyl ester | 68.8 |
| 1, 6-hexanediol diacrylate | 80 |
| Isotridecyl methacrylate | 100 |
| Hydroquinone | 3 |
The preparation steps of the self-leveling light-curing polyurethane resin for synthetic leather of the embodiment are as follows:
1) 630g of polypropylene oxide/ethylene oxide ether triol, 68g of polypropylene oxide ether glycol and 5g of hydroxyl-terminated tetrafunctional organic silicon modified polyether are put into a reaction kettle and are uniformly stirred at 50-55 ℃;
2) 49.4g of diphenylmethane diisocyanate and 34.4g of toluene diisocyanate are put into a reaction kettle in batches, the reaction temperature is strictly controlled to be 75-80 ℃, after 5 hours of normal pressure reaction, sampling is carried out every half an hour to determine the NCO content, when the NCO content is lower than 2.1%, 68.8g of blocking agent hydroxyethyl acrylate and 3g of polymerization inhibitor hydroquinone are put into the reaction kettle, the reaction is continued at 75-80 ℃, when the NCO content is zero, heating is stopped, the reaction kettle is cooled to be lower than 40 ℃, 80g of 1, 6-hexanediol diacrylate and 100g of isotridecyl methacrylate are put into the reaction kettle, and the self-leveling light-cured polyurethane resin for synthetic leather can be obtained after uniform mixing.
Mixing 100g of the obtained resin and 1.5g of photoinitiator Darocur-1173 by a dispersion machine, then coating about 0.2mm on release paper by blade coating, and curing by a UV curing machine; the obtained adhesive film has good leveling property, is folding-resistant at normal temperature, and does not crack for 20 ten thousand times, and does not crack for 8 ten thousand times at the temperature of minus 20 ℃.
Example 10
The raw materials and weights used in this example are shown in Table 10.
Watch 10
| Name of raw materials | Weight (unit: gram) |
| Polypropylene oxide Ether diol (number average molecular weight 2000) | 690 |
| Hydroxyl-terminated tetrafunctional silicone modified polyether (number average molecular weight 6000) | 6 |
| Toluene diisocyanate | 122 |
| Hydroxypropyl acrylate | 110 |
| 1, 6-hexanediol diacrylate | 30 |
| Glycidyl methacrylate | 30 |
| Isobornyl acrylate | 60 |
| Hydroquinone | 3 |
The preparation steps of the self-leveling light-curing polyurethane resin for synthetic leather of the embodiment are as follows:
1) putting 690g of polypropylene oxide ether glycol and 6g of hydroxyl-terminated tetrafunctional organic silicon modified polyether into a reaction kettle, and stirring at 50-55 ℃;
2) 122g of toluene diisocyanate is put into a reaction kettle in batches, the reaction temperature is strictly controlled to be 75-80 ℃, after the reaction is carried out for 4 hours under normal pressure, sampling is carried out every half hour to measure the NCO content, when the NCO content is lower than 3.6%, 110g of end-capping agent hydroxypropyl acrylate and 3g of polymerization inhibitor hydroquinone are put into the reaction kettle, the reaction is carried out at 75-80 ℃, when the NCO content is zero, heating is stopped, the reaction kettle is cooled to be lower than 40 ℃, 30g of 1, 6-hexanediol diacrylate, 30g of glycidyl methacrylate and 60g of isobornyl acrylate are put into the reaction kettle, and the self-leveling photocuring polyurethane resin for synthetic leather can be obtained after uniform mixing.
Mixing 100g of the obtained resin and 1.5g of photoinitiator Darocur-1173 by a dispersion machine, then coating about 0.2mm on release paper by blade coating, and curing by a UV curing machine; the obtained adhesive film has good leveling property, is folding-resistant at normal temperature, and does not crack for 15 ten thousand times, and does not crack for 4 ten thousand times at the temperature of minus 20 ℃.
In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.
Claims (9)
1. The self-leveling light-cured polyurethane resin for the synthetic leather is characterized by being prepared from the following raw materials: polyol, organosilicon modified polyether polyol, diisocyanate, a blocking agent, a common diluent and a low surface energy diluent;
the organic silicon modified polyether polyol is selected from one of hydroxyl-terminated single-functionality organic silicon modified polyether, hydroxyl-terminated two-functionality organic silicon modified polyether, hydroxyl-terminated four-functionality organic silicon modified polyether and side hydroxyl two-functionality organic silicon modified polyether;
the dosage of the organic silicon modified polyether glycol is 0.5 to 1.5 percent of the total weight of the resin;
the low surface energy diluent is selected from one or more of 3,3, 5-trimethylcyclohexyl acrylate, lauric acid acrylate, isodecyl acrylate, isotridecyl methacrylate and isobornyl acrylate;
the dosage of the common diluent and the low surface energy diluent is 10 to 25 percent of the total weight of the polyol, the organosilicon modified polyether polyol, the diisocyanate and the end-capping agent;
the polyhydric alcohol is selected from one or more of polypropylene oxide/ethylene oxide ether triol, polypropylene oxide ether triol, polytetrahydrofuran ether diol, polypropylene oxide/ethylene oxide ether diol, polycaprolactone diol, poly neopentyl glycol adipate diol and poly hexanediol adipate diol, and the polyhydric alcohol necessarily contains polypropylene oxide ether diol and/or polypropylene oxide/ethylene oxide ether diol; the number average molecular weight of the polyol is 500-.
2. The self-leveling light-curing polyurethane resin for synthetic leather according to claim 1, further comprising a polymerization inhibitor.
3. The self-leveling light-curing polyurethane resin for synthetic leather according to claim 2, wherein the amount of the polymerization inhibitor is 0.2-0.5% of the total weight of the resin;
the ratio of the total moles of diisocyanate to the total moles of polyol is 1.5-3: 1;
the ratio of the total number of moles of the blocking agent to the total number of moles of the diisocyanate is 0.9-1.5: 1.
4. The self-leveling light-curing polyurethane resin for synthetic leather according to claim 1 or 2, wherein the end-capping agent is one or more selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
5. The self-leveling light-curable polyurethane resin for synthetic leather according to claim 1 or 2, wherein the common diluent is one or more selected from hydroxyethyl acrylate, hydroxypropyl acrylate, isooctyl acrylate, glycidyl methacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate and trimethylolpropane triacrylate.
6. The self-leveling photocurable polyurethane resin for synthetic leather according to claim 1 or 2, wherein the diisocyanate is at least two selected from the group consisting of toluene diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane 4, 4' -diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate.
7. The self-leveling light-curable polyurethane resin for synthetic leather according to claim 6, wherein the diisocyanate is one or two selected from diphenylmethane 4, 4' -diisocyanate, toluene diisocyanate, and 1, 6-hexamethylene diisocyanate.
8. The method for preparing the self-leveling light-curing polyurethane resin for synthetic leather according to any one of claims 1 to 7, characterized by comprising the following steps:
1) mixing a polyol and a silicone modified polyether polyol;
2) adding diisocyanate for reaction, adding a blocking agent and a polymerization inhibitor, cooling when the NCO content is zero, adding a diluent, and mixing to obtain the self-leveling photocuring polyurethane resin for the synthetic leather.
9. The method of claim 8, wherein:
1) mixing the polyol and the organic silicon modified polyether polyol, and stirring at 50-60 ℃;
2) adding diisocyanate, reacting at 65-80 ℃ under normal pressure for 2-8 hours, adding a blocking agent and a polymerization inhibitor, cooling to below 40 ℃ when the NCO content is zero, adding a diluent, and mixing.
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| CN110467842A (en) * | 2019-07-30 | 2019-11-19 | 清远市美佳乐环保新材股份有限公司 | There is one kind wetting to thicken multifunctional aqueous auxiliary agent and preparation method thereof |
| CN110606930A (en) * | 2019-10-29 | 2019-12-24 | 兰州科天水性高分子材料有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
| CN113897121B (en) * | 2021-10-18 | 2022-08-09 | 上海昶瀚科技有限公司 | Yellowing-resistant self-repairing coating composition, automobile paint protective film and preparation method thereof |
| CN113956784A (en) * | 2021-10-18 | 2022-01-21 | 丽水学院 | Water-based visible light driven film-forming finishing agent for ecological synthetic leather |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416443A (en) * | 2000-01-14 | 2003-05-07 | Dsm有限公司 | Photocurable resin compsn. and optical parts |
| US6562881B2 (en) * | 2001-05-30 | 2003-05-13 | Henkel Loctite Corporation | Liquified polyols, urethane acrylate resins prepared therewith and curable compositions employing such resins |
| CN101311296A (en) * | 2007-05-22 | 2008-11-26 | 比亚迪股份有限公司 | Ultraviolet cured paint composition for vacuum coating |
| CN101463221A (en) * | 2007-12-18 | 2009-06-24 | 赢创德固赛有限责任公司 | Dual cure formulations with components comprising uretdione groups |
| CN101974307A (en) * | 2010-08-13 | 2011-02-16 | 上海材料研究所 | Polyurethane acrylate adhesive containing ionic groups and preparation method thereof |
| CN102304341A (en) * | 2011-06-23 | 2012-01-04 | 太原理工大学 | Preparation method of ultraviolet light curing adhesive |
| CN102634035A (en) * | 2012-03-30 | 2012-08-15 | 南京工业大学 | Organic silicon polyether polyol and preparation method thereof and method for preparing polyurethane elastomer |
| CN102746787A (en) * | 2012-06-25 | 2012-10-24 | 北方涂料工业研究设计院 | Optical fiber coating paint transmittable for deep ultraviolet light |
| CN103436213A (en) * | 2013-09-09 | 2013-12-11 | 烟台德邦科技有限公司 | Ultraviolet-curing type optical resin adhesive and preparation method thereof |
| CN103772618A (en) * | 2013-12-31 | 2014-05-07 | 东莞市宏达聚氨酯有限公司 | Acrylate modified polyurethane resin for leather finish and preparation method thereof |
| CN103937437A (en) * | 2013-01-21 | 2014-07-23 | 达兴材料股份有限公司 | Photocurable polysiloxane urethane (meth) acrylate composition, adhesive, and cured product |
| CN104387551A (en) * | 2014-10-30 | 2015-03-04 | 广州市回天精细化工有限公司 | Preparation method and application of impact-resistant polyurethane acrylate |
| CN104448205A (en) * | 2014-12-24 | 2015-03-25 | 四川达威科技股份有限公司 | Waterborne polyurethane, as well as preparation method and application thereof in coating agent |
| CN104744980A (en) * | 2013-12-31 | 2015-07-01 | 比亚迪精密制造有限公司 | Modified UV paint and preparation method thereof |
| CN104765251A (en) * | 2014-11-06 | 2015-07-08 | 青岛科技大学 | High-toughness photosensitive resin for 3D printing and preparation method thereof. |
| CN105086916A (en) * | 2015-08-05 | 2015-11-25 | 天津沃尔提莫新材料技术有限公司 | High-light-transmittance UV-moisture dual-curing adhesive |
| CN106750140A (en) * | 2016-12-08 | 2017-05-31 | 天津久日新材料股份有限公司 | A kind of amine modified urethane acrylate light-cured resin and preparation method thereof |
| CN107353865A (en) * | 2017-06-21 | 2017-11-17 | 深圳市百丽春粘胶实业有限公司 | A kind of modified polyurethane acrylic resin and preparation method thereof |
| CN107698735A (en) * | 2017-10-31 | 2018-02-16 | 广东丽格科技股份有限公司 | A kind of low-viscosity polyester resin and its preparation method and application |
| CN108409971A (en) * | 2018-02-07 | 2018-08-17 | 江西三越新材料有限公司 | A kind of preparation method of organosilicon modified polyether polyalcohol |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6906136B2 (en) * | 2003-04-22 | 2005-06-14 | Arco Chemical Technology, L.P. | UV-curable compositions |
| US8153195B2 (en) * | 2006-09-09 | 2012-04-10 | Electronics For Imaging, Inc. | Dot size controlling primer coating for radiation curable ink jet inks |
| KR101001656B1 (en) * | 2008-08-26 | 2010-12-15 | 에스에스씨피 주식회사 | Radiation curable resin composition and optical fiber made by using thereof |
| JP5068793B2 (en) * | 2009-09-24 | 2012-11-07 | リンテック株式会社 | Adhesive sheet |
| KR20120072163A (en) * | 2010-12-23 | 2012-07-03 | 제일모직주식회사 | Adhesive film for optically clear adhesive film |
| KR101362869B1 (en) * | 2010-12-29 | 2014-02-14 | 제일모직주식회사 | Adhesive composition for optical film |
| CN105802483B (en) * | 2016-03-29 | 2017-11-07 | 张家港康得新光电材料有限公司 | A kind of double curing coating and preparation method and application |
| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
-
2018
- 2018-12-05 CN CN201811479822.7A patent/CN109666127B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416443A (en) * | 2000-01-14 | 2003-05-07 | Dsm有限公司 | Photocurable resin compsn. and optical parts |
| US6562881B2 (en) * | 2001-05-30 | 2003-05-13 | Henkel Loctite Corporation | Liquified polyols, urethane acrylate resins prepared therewith and curable compositions employing such resins |
| CN101311296A (en) * | 2007-05-22 | 2008-11-26 | 比亚迪股份有限公司 | Ultraviolet cured paint composition for vacuum coating |
| CN101463221A (en) * | 2007-12-18 | 2009-06-24 | 赢创德固赛有限责任公司 | Dual cure formulations with components comprising uretdione groups |
| CN101974307A (en) * | 2010-08-13 | 2011-02-16 | 上海材料研究所 | Polyurethane acrylate adhesive containing ionic groups and preparation method thereof |
| CN102304341A (en) * | 2011-06-23 | 2012-01-04 | 太原理工大学 | Preparation method of ultraviolet light curing adhesive |
| CN102634035A (en) * | 2012-03-30 | 2012-08-15 | 南京工业大学 | Organic silicon polyether polyol and preparation method thereof and method for preparing polyurethane elastomer |
| CN102746787A (en) * | 2012-06-25 | 2012-10-24 | 北方涂料工业研究设计院 | Optical fiber coating paint transmittable for deep ultraviolet light |
| CN103937437A (en) * | 2013-01-21 | 2014-07-23 | 达兴材料股份有限公司 | Photocurable polysiloxane urethane (meth) acrylate composition, adhesive, and cured product |
| CN103436213A (en) * | 2013-09-09 | 2013-12-11 | 烟台德邦科技有限公司 | Ultraviolet-curing type optical resin adhesive and preparation method thereof |
| CN103772618A (en) * | 2013-12-31 | 2014-05-07 | 东莞市宏达聚氨酯有限公司 | Acrylate modified polyurethane resin for leather finish and preparation method thereof |
| CN104744980A (en) * | 2013-12-31 | 2015-07-01 | 比亚迪精密制造有限公司 | Modified UV paint and preparation method thereof |
| CN104387551A (en) * | 2014-10-30 | 2015-03-04 | 广州市回天精细化工有限公司 | Preparation method and application of impact-resistant polyurethane acrylate |
| CN104765251A (en) * | 2014-11-06 | 2015-07-08 | 青岛科技大学 | High-toughness photosensitive resin for 3D printing and preparation method thereof. |
| CN104448205A (en) * | 2014-12-24 | 2015-03-25 | 四川达威科技股份有限公司 | Waterborne polyurethane, as well as preparation method and application thereof in coating agent |
| CN105086916A (en) * | 2015-08-05 | 2015-11-25 | 天津沃尔提莫新材料技术有限公司 | High-light-transmittance UV-moisture dual-curing adhesive |
| CN106750140A (en) * | 2016-12-08 | 2017-05-31 | 天津久日新材料股份有限公司 | A kind of amine modified urethane acrylate light-cured resin and preparation method thereof |
| CN107353865A (en) * | 2017-06-21 | 2017-11-17 | 深圳市百丽春粘胶实业有限公司 | A kind of modified polyurethane acrylic resin and preparation method thereof |
| CN107698735A (en) * | 2017-10-31 | 2018-02-16 | 广东丽格科技股份有限公司 | A kind of low-viscosity polyester resin and its preparation method and application |
| CN108409971A (en) * | 2018-02-07 | 2018-08-17 | 江西三越新材料有限公司 | A kind of preparation method of organosilicon modified polyether polyalcohol |
Non-Patent Citations (2)
| Title |
|---|
| Cheng Jiye，等.Synthesis and properties of photopolymerizable bifunctional polyether-modified polysiloxane polyurethane acrylate prepolymer.《JOURNAL OF ADHESION SCIENCE AND TECHNOLOGY》.2015,第30卷(第1期),第2-12页. * |
| 光聚合型聚硅氧烷改性聚醚聚氨酯丙烯酸酯低聚物的合成、表征与性能;操越，等;《精细化工》;20151231;第32卷(第12期);第1321-1326页 * |
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