One-liquid type polyurethane resin for glitter leather and preparation method of one-liquid type polyurethane resin

Abstract

The invention relates to one-liquid type polyurethane resin for glitter leather and a preparation method of the one-liquid type polyurethane resin. The one-liquid type polyurethane resin for the glitter leather is prepared from the following raw materials: polycarbonate diol, polytetrahydrofuran ether glycol, hydrogenated phenyl methane diisocyanate, a chain extender, a catalyst, diethylenetriamine, dimethyl diethylsilane, divinyl benzene, a solvent, polyether modified heptamethyltrisiloxane, coco fatty acid diethanol amide and amino silicon oil. According to the polyurethane resin, the raw material composition of the polyurethane resin is limited, the dimethyldiethylsilane and the divinyl benzene are used as cross-linking agents, the coco fatty acid diethylamine amide is introduced as an auxiliary agent of the cross-linking agents, and the polyether modified heptamethyltrisiloxane is used as a modifier, so that the cross-linking density of the polyurethane resin can be improved; furthermore, the wear resistance of the prepared polyurethane synthetic leather is improved, and the wear resistance of the prepared glitter leather is ensured.

Description

Technical Field

[0001] The invention belongs to the field of polyurethane resin preparation, and particularly relates to a one-liquid polyurethane resin for glitter leather and a preparation method thereof. Background Art

[0002] Glitter leather, also known as glittered glitter, is a new type of leather material. Its main components include polyester and resin, and its surface is coated with a layer of glitter powder, creating a dazzling shimmering effect under light. It is widely used in decorative applications. The production process of glittered leather typically involves first applying a layer of adhesive to the polyurethane artificial leather, then spraying the glitter powder on it, flattening it appropriately, and drying it.

[0003] Existing polyurethane resins for polyurethane synthetic leather are divided into two categories: one-component polyurethane resins and two-component polyurethane resins. One-component polyurethane resins do not require additional additives and can be used directly, which is more convenient. However, the polyurethane synthetic leather prepared using them has defects such as poor elasticity and wear resistance, which affects the use of the subsequently prepared glitter leather and needs further improvement. Summary of the Invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a one-liquid polyurethane resin for glitter leather and a preparation method thereof.

[0005] The present invention adopts the following technical solutions: The one-liquid polyurethane resin for glitter leather comprises the following raw materials in parts by weight: 20-30 parts of polycarbonate diol, 30-60 parts of polytetramethylene ether glycol, 10-30 parts of hydrogenated phenylmethane diisocyanate, 6-10 parts of a chain extender, 0.5-0.8 parts of a catalyst, 2-3 parts of diethylenetriamine, 2-3 parts of dimethyldiethylsilane, 1-2 parts of divinylbenzene, 60-70 parts of a solvent, 1-2 parts of polyether-modified heptamethyltrisiloxane, 1-2 parts of coconut acid diethanolamide, 3-5 parts of amino silicone oil, and 0.5-1 part of 2-hydroxy-4-octyloxybenzophenone.

[0006] Furthermore, the chain extender is composed of dimethylol propionic acid, ethanolamine, and neopentyl glycol in a mass ratio of 1:0.4-0.5:0.1-0.2.

[0007] Furthermore, the solvent is composed of butanone and petroleum ether in a mass ratio of 1:0.2-0.3.

[0008] Furthermore, the catalyst is dibutyltin dilaurate.

[0009] Furthermore, the molecular weight of the polycarbonate diol is 2000, and the molecular weight of the polytetramethylene ether diol is 2000.

[0010] The preparation method of a one-component polyurethane resin for glitter leather specifically comprises the following steps: Step 1: Add polycarbonate diol and polytetramethylene glycol to a reaction kettle, heat to 90-110° C., vacuum dehydrate for 20-30 minutes, then cool to 45-55° C., add half the amount of hydrogenated phenylmethane diisocyanate, stir evenly, heat to 75-85° C., and keep warm for 1-2 hours; Step 2: Cool the mixture to 45-55°C, add the remaining hydrogenated phenylmethane diisocyanate, chain extender, catalyst, dimethyldiethylsilane, divinylbenzene, polyether-modified heptamethyltrisiloxane, coconut oil diglycol and half the solvent into the reaction kettle, then heat the mixture to 80-90°C and react for 1-1.5 hours to obtain a primary polymer; Step 3: Cool the mixture to 30-40°C, add amino silicone oil and 2-hydroxy-4-octyloxybenzophenone to the reaction kettle, stir evenly, and keep the mixture warm for 1-2 hours to obtain a prepolymer; Step 4: continue to add diethylenetriamine and the remaining solvent into the reactor, mix and stir for 50-70 minutes to obtain the one-component polyurethane resin for glitter leather.

[0011] From the above description of the present invention, it can be seen that compared with the prior art, the beneficial effects of the present invention are as follows: the present application limits the raw material composition of the polyurethane resin, uses dimethyldiethylsilane and divinylbenzene as cross-linking agents, introduces cocoyl diethylamine amide as an auxiliary agent for the cross-linking agent, and polyether-modified heptamethyltrisiloxane as a modifier, which can increase the cross-linking density of the polyurethane resin, thereby improving the wear resistance of the prepared polyurethane synthetic leather and ensuring the wear resistance of the prepared glitter leather; in addition, amino silicone oil, 2-hydroxy-4-octyloxybenzophenone and other components are introduced to improve the flexibility of the polyurethane synthetic leather prepared using the polyurethane resin defined in this application, so that the glitter leather prepared based on the above-mentioned polyurethane synthetic leather has excellent wear resistance and flexibility, thereby ensuring the use of glitter leather.

[0012] The composition of the chain extender is further limited to dimethylolpropionic acid, ethanolamine, neopentyl glycol, dimethyldiethylsilane, and divinylbenzene, so as to increase the crosslinking degree of the polyurethane resin, form a stable network structure inside it, effectively improve the wear resistance of the prepared polyurethane synthetic leather, and meet the required production needs. DETAILED DESCRIPTION

[0013] The present invention is further described below through specific embodiments.

[0014] The one-liquid polyurethane resin for glitter leather comprises the following raw materials in parts by weight: 20-30 parts of polycarbonate diol, 30-60 parts of polytetramethylene ether glycol, 10-30 parts of hydrogenated phenylmethane diisocyanate, 6-10 parts of a chain extender, 0.5-0.8 parts of dibutyltin dilaurate, 2-3 parts of diethylenetriamine, 2-3 parts of dimethyldiethylsilane, 1-2 parts of divinylbenzene, 60-70 parts of a solvent, 1-2 parts of polyether-modified heptamethyltrisiloxane, 1-2 parts of coconut acid diethanolamide, 3-5 parts of amino silicone oil, and 0.5-1 part of 2-hydroxy-4-octyloxybenzophenone.

[0015] The chain extender is composed of dimethylol propionic acid, ethanolamine and neopentyl glycol in a mass ratio of 1:0.4-0.5:0.1-0.2.

[0016] The solvent is composed of butanone and petroleum ether in a mass ratio of 1:0.2-0.3.

[0017] The molecular weight of the polycarbonate diol is 2000, and the molecular weight of the polytetramethylene ether diol is 2000.

[0018] The preparation method of a one-component polyurethane resin for glitter leather specifically comprises the following steps: Step 1: Add polycarbonate diol and polytetramethylene glycol to a reaction kettle, heat to 90-110° C., vacuum dehydrate for 20-30 minutes, then cool to 45-55° C., add half the amount of hydrogenated phenylmethane diisocyanate, stir evenly, heat to 75-85° C., and keep warm for 1-2 hours; Step 2: Cool the mixture to 45-55°C, add the remaining hydrogenated phenylmethane diisocyanate, chain extender, dibutyltin dilaurate, dimethyldiethylsilane, divinylbenzene, polyether-modified heptamethyltrisiloxane, coconut oil diglycol and half the solvent into the reaction kettle, then heat the mixture to 80-90°C and react for 1-1.5 hours to obtain a primary polymer; Step 3: Cool the mixture to 30-40°C, add amino silicone oil and 2-hydroxy-4-octyloxybenzophenone to the reaction kettle, stir evenly, and keep the mixture warm for 1-2 hours to obtain a prepolymer; Step 4: continue to add diethylenetriamine and the remaining solvent into the reactor, mix and stir for 50-70 minutes to obtain the one-component polyurethane resin for glitter leather.

[0019] Example 1 The one-liquid polyurethane resin for glitter leather includes the following raw materials in parts by weight: 20.6 kg of polycarbonate diol, 58.5 kg of polytetramethylene ether glycol, 16.3 kg of hydrogenated phenylmethane diisocyanate, 6.6 kg of chain extender, 0.5 kg of dibutyltin dilaurate, 2.8 kg of diethylenetriamine, 2 kg of dimethyldiethylsilane, 2 kg of divinylbenzene, 60 kg of solvent, 2 kg of polyether-modified heptamethyltrisiloxane, 1 kg of coconut acid diethanolamide, 5 kg of amino silicone oil, and 1 kg of 2-hydroxy-4-octyloxybenzophenone.

[0020] The chain extender is composed of dimethylol propionic acid, ethanolamine and neopentyl glycol in a mass ratio of 1:0.4:0.2.

[0021] The solvent is composed of butanone and petroleum ether in a mass ratio of 1:0.2.

[0022] The molecular weight of the polycarbonate diol is 2000, and the molecular weight of the polytetramethylene ether diol is 2000.

[0023] The preparation method of a one-component polyurethane resin for glitter leather specifically comprises the following steps: Step 1: Add polycarbonate diol and polytetramethylene glycol to a reaction kettle, heat to 90°C, vacuum dehydrate for 30 minutes, then cool to 45°C, add half the amount of hydrogenated phenylmethane diisocyanate, stir evenly, heat to 75°C, and keep warm for 2 hours; Step 2: Cool the mixture to 45°C, add the remaining hydrogenated phenylmethane diisocyanate, chain extender, dibutyltin dilaurate, dimethyldiethylsilane, divinylbenzene, polyether-modified heptamethyltrisiloxane, coconut oil diglycol and half the solvent into the reaction kettle, then heat the mixture to 80°C and react for 1.5 hours to obtain a primary polymer; Step 3: Cool the mixture to 30° C., add amino silicone oil and 2-hydroxy-4-octyloxybenzophenone to the reaction kettle, stir evenly, and keep the mixture warm for 2 hours to obtain a prepolymer; Step 4: continue to add diethylenetriamine and the remaining solvent into the reactor, mix and stir for 50 minutes to obtain the one-liquid polyurethane resin for glitter leather.

[0024] Example 2 The one-liquid polyurethane resin for Glitter Leather comprises the following raw materials in parts by weight: 26.3 kg of polycarbonate diol, 46.2 kg of polytetramethylene ether glycol, 28.6 kg of hydrogenated phenylmethane diisocyanate, 9.8 kg of chain extender, 0.8 kg of dibutyltin dilaurate, 2.1 kg of diethylenetriamine, 3 kg of dimethyldiethylsilane, 1 kg of divinylbenzene, 70 kg of solvent, 1 kg of polyether-modified heptamethyltrisiloxane, 2 kg of coconut acid diethanolamide, 3 kg of amino silicone oil, and 0.5 kg of 2-hydroxy-4-octyloxybenzophenone.

[0025] The chain extender is composed of dimethylol propionic acid, ethanolamine and neopentyl glycol in a mass ratio of 1:0.5:0.1.

[0026] The solvent is composed of butanone and petroleum ether in a mass ratio of 1:0.3.

[0027] The molecular weight of the polycarbonate diol is 2000, and the molecular weight of the polytetramethylene ether diol is 2000.

[0028] The preparation method of a one-component polyurethane resin for glitter leather specifically comprises the following steps: Step 1: Add polycarbonate diol and polytetramethylene glycol to a reaction kettle, heat to 110° C., vacuum dehydrate for 20 minutes, then cool to 55° C., add half the amount of hydrogenated phenylmethane diisocyanate, stir evenly, heat to 85° C., and keep warm for 1 hour; Step 2: Cool the mixture to 55°C, add the remaining hydrogenated phenylmethane diisocyanate, chain extender, dibutyltin dilaurate, dimethyldiethylsilane, divinylbenzene, polyether-modified heptamethyltrisiloxane, coconut oil diglycol and half the solvent into the reaction kettle, then heat the mixture to 90°C and react for 1 hour to obtain a primary polymer; Step 3: Cool the mixture to 40° C., add amino silicone oil and 2-hydroxy-4-octyloxybenzophenone to the reaction kettle, stir evenly, and keep the mixture warm for 1 hour to obtain a prepolymer; Step 4: continue to add diethylenetriamine and the remaining solvent into the reactor, mix and stir for 70 minutes, and obtain the one-liquid polyurethane resin for glitter leather.

[0029] Example 3 The one-liquid polyurethane resin for Glitter Leather comprises the following raw materials in parts by weight: 29.2 kg of polycarbonate diol, 52.4 kg of polytetramethylene ether glycol, 21.5 kg of hydrogenated phenylmethane diisocyanate, 8.1 kg of chain extender, 0.65 kg of dibutyltin dilaurate, 2.6 kg of diethylenetriamine, 2.5 kg of dimethyldiethylsilane, 2.5 kg of divinylbenzene, 65 kg of solvent, 1.5 kg of polyether-modified heptamethyltrisiloxane, 1.5 kg of coconut acid diethanolamide, 4 kg of amino silicone oil, and 0.8 kg of 2-hydroxy-4-octyloxybenzophenone.

[0030] The chain extender is composed of dimethylol propionic acid, ethanolamine and neopentyl glycol in a mass ratio of 1:0.45:0.15.

[0031] The solvent is composed of butanone and petroleum ether in a mass ratio of 1:0.25.

[0032] The molecular weight of the polycarbonate diol is 2000, and the molecular weight of the polytetramethylene ether diol is 2000.

[0033] The preparation method of a one-component polyurethane resin for glitter leather specifically comprises the following steps: Step 1: Add polycarbonate diol and polytetramethylene glycol to a reactor, heat to 100°C, vacuum dehydrate for 25 minutes, then cool to 50°C, add half the amount of hydrogenated phenylmethane diisocyanate, stir evenly, heat to 80°C, and keep the reaction for 1.5 hours; Step 2: Cool the mixture to 50°C, add the remaining hydrogenated phenylmethane diisocyanate, chain extender, dibutyltin dilaurate, dimethyldiethylsilane, divinylbenzene, polyether-modified heptamethyltrisiloxane, coconut oil diglycol and half the solvent into the reaction kettle, then heat the mixture to 85°C and react for 1.2 hours to obtain a primary polymer; Step 3: Cool the mixture to 35°C, add amino silicone oil and 2-hydroxy-4-octyloxybenzophenone to the reaction kettle, stir evenly, and keep the mixture warm for 1.5 hours to obtain a prepolymer; Step 4: continue to add diethylenetriamine and the remaining solvent into the reactor, mix and stir for 60 minutes to obtain the one-component polyurethane resin for glitter leather.

[0034] Comparative Example 1 The raw material composition and preparation method are basically the same as those of Example 3, except that the raw material composition does not include polyether-modified heptamethyltrisiloxane.

[0035] Comparative Example 2 The raw material composition and preparation method are basically the same as those in Example 3, except that the raw material composition does not include coconut oil diethanolamide.

[0036] The polyurethane resins obtained in Examples 1-3 and Comparative Examples 1-2 were used to make polyurethane synthetic leathers. The polyurethane synthetic leathers obtained in each example were subjected to wear resistance tests. Specific results are shown in Table 1. The wear resistance was compared with the requirements of Class I-3 in QB / T 4195-2011.

[0037] Table 1 Performance test table of each embodiment It can be seen from the above table that the glitter leather made of the one-component polyurethane resin defined in the present application has excellent wear resistance.

[0038] The present application limits the raw material composition of the polyurethane resin, uses dimethyldiethylsilane and divinylbenzene as cross-linking agents, introduces cocoyl diethylamine amide as an auxiliary agent for the cross-linking agent, and polyether-modified heptamethyltrisiloxane as a modifier, thereby increasing the cross-linking density of the polyurethane resin, thereby increasing the wear resistance of the prepared polyurethane synthetic leather, and ensuring the wear resistance of the prepared glitter leather; in addition, amino silicone oil, 2-hydroxy-4-octyloxybenzophenone and other components are introduced to improve the flexibility of the polyurethane synthetic leather prepared using the polyurethane resin defined in the present application, so that the glitter leather prepared based on the above-mentioned polyurethane synthetic leather has excellent wear resistance and flexibility, thereby ensuring the use of the glitter leather.

[0039] The above description is merely a preferred embodiment of the present invention and therefore cannot be used to limit the scope of the present invention. In other words, equivalent changes and modifications made according to the scope of the present invention and the contents of the specification should still fall within the scope of the present invention.

Claims

1. One-component polyurethane resin for glitter leather, characterized by: The invention comprises the following raw materials in parts by weight: 20-30 parts of polycarbonate diol, 30-60 parts of polytetramethylene ether glycol, 10-30 parts of hydrogenated phenylmethane diisocyanate, 6-10 parts of a chain extender, 0.5-0.8 parts of a catalyst, 2-3 parts of diethylenetriamine, 2-3 parts of dimethyldiethylsilane, 1-2 parts of divinylbenzene, 60-70 parts of a solvent, 1-2 parts of polyether-modified heptamethyltrisiloxane, 1-2 parts of coconut acid diethanolamide, 3-5 parts of amino silicone oil, and 0.5-1 part of 2-hydroxy-4-octyloxybenzophenone.

2. The one-component polyurethane resin for glitter leather according to claim 1, characterized in that: The chain extender is composed of dimethylol propionic acid, ethanolamine and neopentyl glycol in a mass ratio of 1:0.4-0.5:0.1-0.

2.

3. The one-component polyurethane resin for glitter leather according to claim 1, characterized in that: The solvent is composed of butanone and petroleum ether in a mass ratio of 1:0.2-0.

3.

4. The one-component polyurethane resin for glitter leather according to claim 1, characterized in that: The catalyst is dibutyltin dilaurate.

5. The one-component polyurethane resin for glitter leather according to claim 1, characterized in that: The molecular weight of the polycarbonate diol is 2000, and the molecular weight of the polytetramethylene ether diol is 2000.

6. The method for preparing the one-component polyurethane resin for glitter leather according to claim 1, wherein: The specific steps include: Step 1: Add polycarbonate diol and polytetramethylene glycol to a reaction kettle, heat to 90-110° C., vacuum dehydrate for 20-30 minutes, then cool to 45-55° C., add half the amount of hydrogenated phenylmethane diisocyanate, stir evenly, heat to 75-85° C., and keep warm for 1-2 hours; Step 2: Cool the mixture to 45-55°C, add the remaining hydrogenated phenylmethane diisocyanate, chain extender, catalyst, dimethyldiethylsilane, divinylbenzene, polyether-modified heptamethyltrisiloxane, coconut oil diglycol and half the solvent into the reaction kettle, then heat the mixture to 80-90°C and react for 1-1.5 hours to obtain a primary polymer; Step 3: Cool the mixture to 30-40°C, add amino silicone oil and 2-hydroxy-4-octyloxybenzophenone to the reaction kettle, stir evenly, and keep the mixture warm for 1-2 hours to obtain a prepolymer; Step 4: continue to add diethylenetriamine and the remaining solvent into the reactor, mix and stir for 50-70 minutes to obtain the one-component polyurethane resin for glitter leather.

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