Full-bio-based scratch-resistant matting coating agent as well as preparation method and application thereof

Abstract

The invention provides a full bio-based scratch-resistant matting coating agent, which is prepared from the following ingredients in parts by weight: 5 to 20 parts of bio-based polyhydric alcohol, 1 to 15 parts of bio-based dihydric alcohol, 0.5 to 5 parts of bio-based diamine, 3 to 20 parts of bio-based diisocyanate, 0.5 to 5 parts of bio-based matting agents and 60 to 90 parts of bio-based solvents. According to the full-bio-based scratch-resistant matting coating agent, full-bio-based polyurethane is synthesized from bio-based polyhydric alcohol, bio-based dihydric alcohol, bio-based diamine and bio-based diisocyanate, then a bio-based matting agent is added, the mixture is dissolved in a bio-based solvent or water, and a finished product of the full-bio-based scratch-resistant matting coating agent is obtained. The physical performance of the material is basically consistent with the performance of a conventional petrochemical product, and the material has good wear resistance and scratch resistance and can meet or exceed the performance requirements of the conventional product. The invention also provides a preparation method and application of the full-bio-based scratch-resistant matting coating agent.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material synthesis, and particularly relates to a fully bio-based scratch-resistant matt coating agent, a preparation method thereof, and an application thereof. Background Art

[0002] Currently, with the implementation of China's low-carbon environmental protection policies, polymer material products such as coatings need to develop in the direction of low-carbon and environmental protection. Among them, products based on bio-based raw material components are a key type of development in the field of polymer materials. Under the general background of "dual carbon" and sustainable development, the bio-based materials industry and market are developing rapidly.

[0003] A coating agent refers to a continuous film formed by coating one or more layers of polymer compounds on the surface of a fabric, forming a composite of the fabric and the film. The fabric is called a coated fabric, and the polymer compound is called a coating agent. Currently, most coating agents are mainly based on petrochemical materials. If it is a matt product, petrochemical mattifying agents or mineral mattifying agents need to be added. Since petrochemical materials are non-renewable resources and are not environmentally friendly.

[0004] In the life cycle of products, the degradation problem is a key technical problem. Most petrochemical material products require decades to degrade, and a large number of harmful substances are also produced after degradation. After bio-based materials are discarded, they can be transformed into non-toxic small molecules such as water and carbon dioxide through biological degradation methods such as combustion or composting, and re-enter the natural cycle to maintain the entire ecological balance without worrying about causing environmental pollution.

[0005] Among the reported bio-based coating materials, only some are bio-based and cannot achieve fully bio-based. For example, the Chinese invention patent with the publication number CN105754467A discloses a preparation method of a bio-based polyurethane flame retardant coating, which uses polyol, diisocyanate, ammonium polyphosphate, phytic acid, layered double hydroxide, dimethylolpropionic acid, 1,4-butanediol, and triethylamine as raw materials, and obtains the bio-based polyurethane flame retardant coating through prepolymerization, neutralization, emulsification, and shaping. In this coating, most are still petrochemical materials and only contain some bio-based materials.

[0006] Another example is the Chinese invention patent with the publication number CN116693802A, which discloses a bio-based polyurethane buffer material, including the following raw materials in parts by weight: 30-50 parts of sulfonated linseed oil polyol, 45-65 parts of polyether polyol, 70-100 parts of diisocyanate, 5-10 parts of sulfonate-modified diisocyanate, 0.5-0.7 parts of organotin catalyst, 2-3 parts of amine catalyst, 2-5 parts of foam stabilizer, and 2-4 parts of deionized water. This polyurethane buffer material is a solid TPU material.

[0007] It can be seen that the current applications of bio-based polyurethanes mainly focus on TPU, and there is less involvement in coatings and coating agents. Summary of the Invention

[0008] To solve the above problems existing in the prior art, the present invention provides a fully bio-based scratch-resistant matte coating agent, which synthesizes a fully bio-based polyurethane from bio-based polyols, bio-based diols, bio-based diamines and bio-based diisocyanates, and then adds a bio-based matting agent and dissolves it in a bio-based solvent or water to obtain a fully bio-based scratch-resistant matte coating agent. Its physical properties are basically the same as those of conventional petrochemical products, and it has good abrasion resistance and scratch resistance, and can meet or exceed the performance requirements of conventional products. The present invention also provides a preparation method and application of the fully bio-based scratch-resistant matte coating agent.

[0009] To achieve the above object, the present invention provides the following technical solutions:

[0010] A fully bio-based scratch-resistant matte coating agent, by weight, comprises the following components:

[0011] Bio-based polyol 5 - 20 parts,

[0012] Bio-based diol 1 - 15 parts,

[0013] Bio-based diamine 0.5 - 5 parts,

[0014] Bio-based diisocyanate 3 - 20 parts,

[0015] Bio-based matting agent 0.5 - 5 parts,

[0016] Bio-based solvent 60 - 90 parts.

[0017] In one preferred embodiment, the bio-based polyol is polytetramethylene ether glycol, and by molecular weight, its models include H500, H1000, H2000 and H2700.

[0018] In one preferred embodiment, the bio-based polyol is a polyester polyol, and its models include: PE6056, with a molecular weight of 2000 and 100% bio-based; and PE6656, with a molecular weight of 2000 and 37% bio-based.

[0019] In one preferred embodiment, the bio-based diol is bio-based 1,4-butanediol.

[0020] In one preferred embodiment, the bio-based diamine is bio-based 1,5-pentanediamine.

[0021] In one preferred embodiment, the bio-based diisocyanate is bio-based 1,5-pentane diisocyanate.

[0022] In one preferred embodiment, the bio-based matting agent is at least one of CERAFLOUR 1010 of BYK or CERAFLOUR 929N.

[0023] In one preferred embodiment, the bio-based solvent is Cyrene TM [(-)-dihydrolevoglucosenone] can replace the conventionally used DMF and NMPP, or ethanol and ketone solvents made from cassava or corn

[0024] The present invention also provides a preparation method of the above-mentioned all-bio-based scratch-resistant matting coating agent, and the preparation method includes the following steps:

[0025] S1. By weight, react bio-based polyol, bio-based diol and bio-based diisocyanate at 90-95 °C for 1-4 hours until the NCO value is lower than or close to the theoretical value;

[0026] S2. Cool down to below 50 °C, add bio-based diamine for chain extension to increase the molecular weight to the set value, and judge the molecular weight by measuring the viscosity; during this process, bio-based solvent can be added at each stage to adjust the viscosity until the viscosity and the content of non-volatile matter meet the requirements;

[0027] S3: Further add bio-based solvent and bio-based matting agent to adjust to the working viscosity and the required gloss to obtain the finished product of the bio-based matting coating agent.

[0028] The present invention also provides the application of the above-mentioned all-bio-based scratch-resistant matting coating agent, which uses the above-mentioned all-bio-based scratch-resistant matting coating agent and is applied to the surface treatment of artificial leather, fabric, paper and decorative sheets, and is also applied to inks.

[0029] Based on the above technical solutions, compared with the prior art, the present invention has the following advantages and beneficial effects:

[0030] (1) The all-bio-based scratch-resistant matting coating agent provided by the present invention synthesizes all-bio-based polyurethane from bio-based polyol, bio-based diol, bio-based diamine and bio-based diisocyanate, and then adds a bio-based matting agent and dissolves it in a bio-based solvent or water to obtain an all-bio-based scratch-resistant matting coating agent. Its physical properties are basically the same as those of conventional petrochemical products, and it has good wear resistance and scratch resistance, and can meet or exceed the performance requirements of conventional products.

[0031] (2) The method for preparing the all-bio-based scratch-resistant matte coating agent of the present invention uses all-bio-based materials to prepare the all-bio-based scratch-resistant matte coating agent. The finished product passes the C14 test, reduces carbon footprint and carbon emissions, and its degradation products are water and carbon dioxide, and no other harmful substances are produced. The matte agent does not need to be ground, and has good system compatibility and storage stability.

[0032] (3) The present invention uses all-biobased materials to synthesize polyurethane resin, and uses this all-biobased polyurethane resin material as the basis to manufacture a bio-based matte coating agent, which can be used for surface treatment of artificial leather, fabrics, paper, and decorative sheet surfaces, and can also be used for inks, and can provide different gloss and feel for the surfaces of various materials and increase wear resistance; the product can meet performance requirements and product life cycle and carbon footprint testing, and meet the country's dual-carbon requirements for products. DETAILED DESCRIPTION

[0033] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively below in conjunction with specific embodiments. The present invention provides preferred embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0035] A fully bio-based scratch-resistant matte coating agent comprises the following components by weight: 5-20 parts of bio-based polyol, 1-15 parts of bio-based diol, 0.5-5 parts of bio-based diamine, 3-20 parts of bio-based diisocyanate, 0.5-5 parts of bio-based matting agent and 60-90 parts of bio-based solvent.

[0036] Among them, the bio-based polyol is polytrimethylene ether glycol, and its models include H500, H1000, H2000 and H2700 according to molecular weight.

[0037] Among them, the bio-based polyol is a polyester polyol, which can be the 100% bio-based high-performance polyol PO3G provided by Haoyi New Materials, whose main component is polytrimethylene ether glycol, and its models are divided into H500, H1000, H2000 and H2700 according to molecular weight. Bio-based polyols can also come from Zhejiang Huafeng bio-based polyester polyols, and its models are PE-6056 (molecular weight 2000, 100% bio-based) or PE6656 (molecular weight 2000, 37% bio-based).

[0038] Among them, the bio-based diol is bio-based 1,4-butanediol, and the manufacturers can be selected from DSM, BASF, Mitsubishi Chemical, and Yuanli Chemical.

[0039] Among them, the bio-based diamine is bio-based 1,5-pentanediamine, and the manufacturers can be selected from South Korean food company Daesang and Shanghai Kaisai Biotechnology Co., Ltd.

[0040] Among them, the bio-based diisocyanate is bio-based 1,5-pentane diisocyanate, and the manufacturers can be selected from Covestro and Mitsui Chemicals.

[0041] Among them, the bio-based matting agent is at least one of CERAFLOUR 1010 from BYK company, or CERAFLOUR 929N (60 gloss 5, 10, 2%).

[0042] Among them, the bio-based solvent is Cyrene TM [(-)-dihydrolevoglucosenone] can replace the conventionally used DMF and NMP, or ethanol and ketone solvents made from cassava or corn

[0043] The above-mentioned all-bio-based scratch-resistant matting coating agent is prepared by the following preparation method, and the preparation method specifically includes the following steps:

[0044] S1. By weight, react the bio-based polyol, bio-based diol, and bio-based diisocyanate at 90-95 °C for 1-4 hours until the NCO value is lower than or close to the theoretical value;

[0045] S2. Cool down to below 50 °C, add bio-based diamine for chain extension to increase the molecular weight to the set value, and judge the molecular weight by measuring the viscosity; during this process, bio-based solvent can be added at each stage to adjust the viscosity until the viscosity and the content of non-volatile matter meet the requirements;

[0046] S3: Further add bio-based solvent and bio-based matting agent to adjust to the working viscosity and the required gloss to obtain the finished product of bio-based matting coating agent.

[0047] The prepared all-bio-based scratch-resistant matting coating agent, due to the use of all-bio-based materials, can be recycled and reused, and the waste does not cause secondary pollution, reducing the carbon footprint. In addition, due to the excellent matting effect and wear resistance of the coating, good scratch-resistant matting effects can be obtained when applied to the surface treatment of artificial leather, fabrics, papers, and decorative sheets, as well as when applied to inks.

[0048] Example 1

[0049] This example provides an all-bio-based scratch-resistant matting coating agent, which is prepared by the following preparation method:

[0050] Add 200 g of bio - based polyol H2000 (molecular weight 2000), 36.4 g of bio - based diol 1,4 - butanediol (BDO), and 107.8 g of bio - based diisocyanate 1,5 - pentamethylene diisocyanate (PDI) into a three - necked flask, and react at 90 °C for 2 - 3 hours until the NCO is below 1.16 mmol / g to obtain a prepolymer.

[0051] Cool the prepolymer to 50 °C, and add 344.3 g of bio - based solvent (Cyrene TM ) and slowly dropwise add 20.4 g of bio - based diamine 1,5 - pentanediamine for chain extension. When the viscosity rises to 3000 - 50000 mPa·s, add 1111 g of bio - based alcohol to obtain a bio - based polyurethane resin solution. Finally, add 36.38 g of bio - based matting agent CERAFLOUR 1010, disperse evenly at high speed, and filter through a 20 - mesh sieve to obtain the finished product of the all - bio - based scratch - resistant matting coating agent. After testing, its non - volatile content is 21.6%, the viscosity is 800 mPa·s / 25 °C. Coated on the surface of PU artificial leather, the 600 - brightness drops from 45 to 5, and the touch is soft.

[0052] Example 2

[0053] This example provides an all - bio - based scratch - resistant matting coating agent, which is prepared by the following preparation method:

[0054] Add 200 g of bio - based polyol PE - 6056 (molecular weight 2000), 36.4 g of bio - based diol 1,4 - butanediol (BDO), and 107.8 g of bio - based diisocyanate 1,5 - pentamethylene diisocyanate (PDI) into a three - necked flask, and react at 90 °C for 2 - 3 hours until the NCO is below 1.16 mmol / g to obtain a prepolymer.

[0055] Cool the prepolymer to 50 °C, and add 344.3 g of bio - based solvent (Cyrene TM ) and slowly dropwise add 20.4 g of bio - based diamine 1,5 - pentanediamine for chain extension. When the viscosity rises to 3000 - 50000 mPa·s, add 1111 g of bio - based alcohol to obtain a bio - based polyurethane resin solution. Finally, add 36.38 g of bio - based matting agent CERAFLOUR 1010, disperse evenly at high speed, and filter through a 20 - mesh sieve to obtain the finished product of the all - bio - based scratch - resistant matting coating agent. After testing, its non - volatile content is 21.6%, the viscosity is 1000 mPa·s / 25 °C. Coated on the surface of PU artificial leather, the 600 - brightness drops from 45 to 4.5. Compared with Example 11, the bio - based polyol is changed to polyester - type, and the mechanical properties of the coating film are excellent and the scratch - resistant performance is good.

[0056] Example 3

[0057] This embodiment provides a fully biobased scratch-resistant matte coating agent, which is prepared by the following preparation method:

[0058] Add 200 g of biobased polyol H2000 (molecular weight 2000), 36.4 g of biobased diol 1,4-butanediol (BDO), and 107.8 g of biobased diisocyanate 1,5-pentane diisocyanate (PDI) into a three-necked flask, and react at 90 °C for 2 - 3 hours until the NCO is below 1.16 mmol / g to obtain a prepolymer.

[0059] Cool the prepolymer to 50 °C, and add 344.3 g of biobased solvent (Cyrene TM ) and slowly drop in 20.4 g of biobased diamine 1,5-pentanediamine for chain extension. When the viscosity rises to 3000 - 50000 mPa·s, add 1111 g of biobased alcohol to obtain a biobased polyurethane resin solution. Finally, add 36.38 g of biobased matting agent CERAFLOUR 929N, disperse evenly at high speed, and filter through a 20-mesh sieve to obtain the finished product of the fully biobased scratch-resistant matte coating agent. After testing, its non-volatile content is 21.6%, the viscosity is 800 mPa·s / 25 °C. When coated on the surface of PU artificial leather, the 600 brightness drops from 45 to 7, and the touch is soft. Compared with Example 1, in this embodiment, the biobased matting agent is changed, the matting degree is not high, close to the flat light type product, and the scratch resistance is improved.

[0060] Example 4

[0061] This embodiment provides a fully biobased scratch-resistant matte coating agent, which is prepared by the following preparation method:

[0062] Add 100 g of biobased polyol H2000 (molecular weight 2000), 100 g of biobased polyol PE-6056 (molecular weight 2000), 36.4 g of biobased diol 1,4-butanediol (BDO), and 107.8 g of biobased diisocyanate 1,5-pentane diisocyanate (PDI) into a three-necked flask, and react at 90 °C for 2 - 3 hours until the NCO is below 1.16 mmol / g to obtain a prepolymer.

[0063] Cool the prepolymer to 50 °C, and add the biobased solvent (Cyrene TM) 344.3 g, slowly drop in 20.4 g of bio-based diamine 1,5-pentanediamine for chain extension. When the viscosity rises to 3000 - 50000 mPa·s, add 1111 g of bio-based alcohol to obtain a bio-based polyurethane resin solution. Finally, add 36.38 g of bio-based matting agent CERAFLOUR 1010, disperse uniformly at high speed, and filter through a 20-mesh sieve to obtain the finished product of the all-bio-based scratch-resistant matting coating agent. After testing, its non-volatile content is 21.6%, the viscosity is 800 mPa·s / 25 °C. Coated on the surface of PU artificial leather, the brightness at 600 drops from 45 to 4. In this example, a mixed bio-based polyol is used, and the product is more matting than a single polyol.

[0064] Comparative Example 1

[0065] A matting coating agent is prepared by the following preparation method:

[0066] Add 200 g of polyether polyol N220 (molecular weight 2000), 36.4 g of diol 1,4-butanediol (BDO), and 155.4 g of isophorone diisocyanate (IPDI) to a three-necked flask, and react at 90 °C for 2 - 3 hours until the NCO is below 1.02 mmol / g to obtain a prepolymer.

[0067] Cool the prepolymer to 50 °C, add 344.3 g of solvent DMF, slowly drop in 34 g of diamine IPDA for chain extension. When the viscosity rises to 3000 - 50000 mPa·s, add 1333 g of alcohol to obtain a common petrochemical-type polyurethane resin solution. Finally, add 36.38 g of silica matting agent, disperse uniformly at high speed, and filter through a 20-mesh sieve to obtain the finished product, with a non-volatile content of 21.6% and a viscosity of 800 mPa·s / 25 °C.

[0068] Prepare thin films from the all-bio-based polyurethane resin solutions of Examples 1 - 4 and the polyurethane resin solution of Comparative Example 1 respectively, and conduct mechanical property tests. The test results are shown in Table 1.

[0069] Table 1 Performance test table of thin films prepared from the all-bio-based scratch-resistant matting coating agents of Examples 1 - 4 and the matting coating agent (prepared from conventional petrochemical components) of Comparative Example 1

[0070] Test items Example 1 Example 2 Example 3 Example 4 Comparative Example 1 <![CDATA[Tensile strength (kg / cm 2 )]]> 430 550 430 550 450 Elongation rate (%) 430 450 450 450 400 <![CDATA[100% modulus (kg / cm 2 )]]> 100 110 100 105 100

[0071] It can be seen from the above table results that the mechanical properties of the thin films prepared from the all-bio-based scratch-resistant matting coating agents of Examples 1 - 4 are basically the same as those of the thin films prepared from the matting coating agent prepared by conventional petrochemical methods. The difference is whether the polyol belongs to the polyester type or the polyether type.

[0072] The coatings formed by the fully bio-based scratch-resistant matting coating agents of Examples 1-4 and the matting coating agent of Comparative Example 1 were subjected to gloss and abrasion resistance tests to investigate the factors affecting the matting degree and abrasion of the fully bio-based scratch-resistant coating agent. The test results are shown in Table 2.

[0073] Table 2 Gloss and scratch abrasion resistance performance test table of the fully bio-based scratch-resistant matting coating agents of Examples 1-4 and the matting coating agent of Comparative Example 1 (prepared from conventional petrochemical components)

[0074]

[0075]

[0076] It can be seen from Table 2 that the main factor affecting the matting degree is the type of matting agent. In addition, the mixed polyol also has an impact. The use of a bio-based matting agent greatly improves the abrasion resistance, and the polyester type has better abrasion resistance than the polyether type.

[0077] The above content is only an example and illustration of the present invention. The description is relatively specific and detailed, but it cannot be construed as a limitation on the scope of the present invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these obvious replacement forms all belong to the protection scope of the present invention.

Claims

1. A fully bio-based scratch-resistant matte coating agent, characterized in that By weight parts, it includes the following components: Bio-based polyol: 5 - 20 parts, Bio-based diol: 1 - 15 parts, Bio-based diamine: 0.5 - 5 parts, Bio-based diisocyanate: 3 - 20 parts, Bio-based matting agent: 0.5 - 5 parts, Bio-based solvent: 60 - 90 parts.

2. The all-bio-based scratch-resistant matting coating agent according to claim 1, characterized in that the bio-based polyol is polytetramethylene ether glycol, and according to its molecular weight, its models include H500, H1000, H2000 and H2700.

3. The all-bio-based scratch-resistant matting coating agent according to claim 1, characterized in that the bio-based polyol is polyester polyol, and its models include: PE6056 with a molecular weight of 2000 and 100% bio-based; and PE6656 with a molecular weight of 2000 and 37% bio-based.

4. The all-bio-based scratch-resistant matting coating agent according to claim 1, characterized in that the bio-based diol is bio-based 1,4-butanediol.

5. The all-bio-based scratch-resistant matting coating agent according to claim 1, characterized in that the bio-based diamine is bio-based 1,5-pentanediamine.

6. The all-bio-based scratch-resistant matting coating agent according to claim 1, characterized in that the bio-based diisocyanate is bio-based 1,5-pentane diisocyanate.

7. The all-bio-based scratch-resistant matting coating agent according to claim 1, characterized in that the bio-based matting agent is at least one of CERAFLOUR 1010 or CERAFLOUR 929N of BYK company.

8. The all-bio-based scratch-resistant matting coating agent according to claim 1, characterized in that The bio-based solvent is Cyrene TM [(-)-dihydrolevoglucosenone] can replace commonly used DMF and NMP, or ethanol and ketone solvents made from cassava or corn.

9. A preparation method of the all-bio-based scratch-resistant matte coating agent according to any one of claims 1-8, characterized in that, it includes the following steps: S1. By weight parts, react the bio-based polyol, bio-based diol and bio-based diisocyanate at 90 - 95 °C for 1 - 4 hours until the NCO value is lower than or close to the theoretical value; S2. Cool down to below 50 °C, add the bio-based diamine for chain extension to increase the molecular weight to the set value, and judge the molecular weight by measuring the viscosity; during this process, the bio-based solvent can be added at each stage to adjust the viscosity until the viscosity and the non-volatile content meet the requirements; S3: Further add the bio-based solvent and the bio-based matting agent to adjust to the working viscosity and the required gloss to obtain the finished bio-based matting coating agent.

10. Application of a fully bio-based scratch-resistant matte coating agent, characterized in that, The all-bio-based scratch-resistant matting coating agent according to any one of claims 1 - 8 is used for the surface treatment of artificial leather, fabrics, papers and decorative sheets, and is also used in inks.

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