CN117005213B - Preparation and application of a waterborne polyurethane composite coating with high ductility - Google Patents
Preparation and application of a waterborne polyurethane composite coating with high ductilityInfo
- Publication number
- CN117005213B CN117005213B CN202311002985.7A CN202311002985A CN117005213B CN 117005213 B CN117005213 B CN 117005213B CN 202311002985 A CN202311002985 A CN 202311002985A CN 117005213 B CN117005213 B CN 117005213B
- Authority
- CN
- China
- Prior art keywords
- aqueous polyurethane
- coating
- modulus
- parts
- waterborne polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0009—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using knitted fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/068—Polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention relates to preparation and application of a high-ductility aqueous polyurethane composite coating, which comprises the steps of firstly coating lower aqueous polyurethane slurry on the surface of a target object, drying and curing to form a lower aqueous polyurethane coating, then coating middle aqueous polyurethane slurry on the lower aqueous polyurethane coating, drying and curing to form a middle aqueous polyurethane coating, then coating upper aqueous polyurethane slurry on the middle aqueous polyurethane coating, drying and curing to form an upper aqueous polyurethane coating, and finally standing to obtain the high-ductility aqueous polyurethane composite coating, wherein when the target object for coating is microfiber base cloth, the product is used for preparing superfine fiber PU synthetic leather, and the tensile load of the superfine fiber PU synthetic leather is more than or equal to 540N, and the elongation at break is more than or equal to 60%. The preparation method of the invention obtains the coating material with high strength and high ductility, and the product is used for preparing superfine fiber PU synthetic leather with excellent strength and toughness.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and relates to preparation and application of a high-ductility aqueous polyurethane composite coating.
Background
The polyurethane used for the surface coating of the synthetic leather in the prior art is high-hard-segment-content aqueous polyurethane with good strength, the hard segment content level of the aqueous polyurethane is generally evaluated by adopting 100% modulus, the more the hard segment content is, the greater the 100% modulus is, and the 100% modulus is generally more than or equal to 34MPa so as to meet the strength requirement of the material. However, aqueous polyurethanes with high hard segment contents tend to have insufficient ductility.
In the PU elastomer field, the plasticity of polyurethane materials is increased by adding a small molecular lubricant, so that the ductility is increased, the polyurethane materials have higher ductility and toughness, and the problems of cracking, fracture and the like are not easy to generate in the subsequent processing and using processes. The nano-composite polyether type thermoplastic polyurethane elastomer composition comprises a nano-composite polyether type thermoplastic polyurethane elastomer composition, a micro-molecular lubricant, wherein the micro-molecular lubricant is generally used in an amount of 0.05-5% of the total mass of the formula.
It is more effective to improve ductility by adding small molecule lubricants, which are also suitable for use in the polyurethane coating field. However, for polyurethane substrates of different rigidities, the effect achieved by ductility improvement with small molecule lubricants is different. When the 100% modulus is up to 40MPa, the rigidity of the material is too high, the ideal effect is hardly obtained through a small molecular lubricant, for polyurethane with the 100% modulus of 34-40 MPa, the small molecular lubricant is added to improve the ductility, although the small molecular lubricant is effective, the limit addition level of the water-based polyurethane with high hard segment content is lower, the limit addition amount is about 10%, when the addition amount exceeds the limit value, the ductility modification of the material can not be increased along with the increase of the addition amount, the lubricant can be separated out to the surface after the limit addition amount is exceeded, so that the concentration of the small molecules actually distributed in the matrix is not increased actually, but the appearance problem is caused, the currently commonly applicable means for obtaining the high ductility is to select a polyurethane matrix with lower 100% modulus, and further, the lubricant within 30% can be added, but the means that the high strength and the high ductility material can not be obtained simultaneously, because the lower the 100% modulus of the selected matrix is, the strength is poor, and the ductility improvement of the lubricant can not be improved.
Therefore, a preparation method and application of the aqueous polyurethane coating with excellent strength and toughness are researched to solve the problems, and the aqueous polyurethane coating has very important significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides preparation and application of a high-ductility aqueous polyurethane composite coating.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the aqueous polyurethane composite coating with high ductility comprises the steps of firstly coating lower aqueous polyurethane slurry on the surface of a target, drying and solidifying to form a lower aqueous polyurethane coating, then coating middle aqueous polyurethane slurry on the lower aqueous polyurethane coating, drying and solidifying to form a middle aqueous polyurethane coating, then coating upper aqueous polyurethane slurry on the middle aqueous polyurethane coating, drying and solidifying to form an upper aqueous polyurethane coating, and finally standing to obtain the aqueous polyurethane composite coating with high ductility;
the middle-layer aqueous polyurethane slurry comprises high 100% modulus aqueous polyurethane resin, a small molecule lubricant and water;
the upper layer aqueous polyurethane slurry comprises low 100% modulus aqueous polyurethane resin, a small molecule lubricant and water;
the lower layer aqueous polyurethane slurry comprises low 100% modulus aqueous polyurethane resin, a small molecule lubricant and water;
The 100% modulus of the high 100% modulus aqueous polyurethane resin is 34-40 MPa, and the 100% modulus of the low 100% modulus aqueous polyurethane resin is 1-2 MPa;
The high 100% modulus aqueous polyurethane resin has the same monomer units as the low 100% modulus aqueous polyurethane resin;
In the middle-layer aqueous polyurethane slurry, 100 parts by mass of high 100% modulus aqueous polyurethane resin is correspondingly added with 8-10 parts by mass of small molecular lubricants, the addition amount of the small molecular lubricants is close to a precipitation limit value and still within the precipitation limit, if the small molecular lubricants in the middle-layer aqueous polyurethane exceed the precipitation limit, precipitated oil spots are generated on the surface after film formation, and the small molecular lubricants are aggregates of the small molecular lubricants and are incompatible with the aqueous polyurethane, so that the subsequent process of further coating a qualified composite coating on the surface is difficult. The mass parts of the small molecular lubricant which is added correspondingly to 100 parts by mass of the low 100% modulus aqueous polyurethane resin in the upper aqueous polyurethane slurry and the lower aqueous polyurethane slurry are respectively at least 1.5 times of the mass parts of the small molecular lubricant which is added correspondingly to 100 parts by mass of the low 100% modulus aqueous polyurethane resin in the middle aqueous polyurethane slurry, and when the addition amount of the small molecular lubricant is within the precipitation limit, if the addition amount of the small molecular lubricant is less than 1.5, the concentration of the small molecular lubricant in the high 100% modulus aqueous polyurethane resin is not remarkably improved through concentration difference diffusion, and the ductility of the material is not remarkably improved.
As a preferable technical scheme:
According to the preparation method of the aqueous polyurethane composite coating with high ductility, the thickness ratio of the upper aqueous polyurethane coating to the middle aqueous polyurethane coating is 10:90-17:83, and the thickness of the lower aqueous polyurethane coating is the same as the thickness of the upper aqueous polyurethane coating.
According to the preparation method of the aqueous polyurethane composite coating with high ductility, the thickness of the middle aqueous polyurethane coating is 50-300 mu m, and the thickness of the upper aqueous polyurethane coating is 10-50 mu m.
According to the preparation method of the aqueous polyurethane composite coating with high ductility, the middle aqueous polyurethane slurry comprises, by mass, 100 parts of high 100% modulus aqueous polyurethane resin, 8-10 parts of small molecular lubricants and 70-500 parts of water, the upper aqueous polyurethane slurry comprises, by mass, 100 parts of low 100% modulus aqueous polyurethane resin, 12-22 parts of small molecular lubricants and 70-500 parts of water, and the lower aqueous polyurethane slurry comprises, by mass, 100 parts of low 100% modulus aqueous polyurethane resin, 12-22 parts of small molecular lubricants and 70-500 parts of water;
According to the actual requirement, adjuvants such as thickener can be added, for example, 0.1-1 part of thickener can be added to adjust the viscosity of the aqueous polyurethane paint to 1000 mPa.s to 6000 mPa.s (the test temperature is 25 ℃ by adopting a rotational viscometer), so that the coating can be smoothly carried out, and the thickener can be adopted by stahl company EVO RM-4417EVO RM-4456, these assistants and their functions are all of the prior art. According to actual requirements, a colorant can be added into the upper aqueous polyurethane slurry for color mixing, for example, 1-10 parts of colorant, such as QCS-840 series of Guangzhou colorful new material Co.
According to the preparation method of the aqueous polyurethane composite coating with high ductility, the small molecular lubricant is the triethyl phosphate, and the solubility of the triethyl phosphate in water is large, so that more small molecular lubricants can be added.
The preparation method of the aqueous polyurethane composite coating with high ductility is a conventional coating method, and the coating method is a roll coating method, so that the process parameters can be adjusted according to the target coating thickness by a person skilled in the art.
According to the preparation method of the aqueous polyurethane composite coating with high ductility, the standing temperature is 50-70 ℃, the standing time is more than 48 hours, and the setting of the standing temperature and the standing time is because a certain time is needed to enable a high-concentration small-molecule lubricant to diffuse into polyurethane, the high temperature of 50-70 ℃ can accelerate diffusion, and the difference of the breaking elongation of the composite coating which is not subjected to standing and the breaking elongation of the composite coating after standing is large.
According to the preparation method of the aqueous polyurethane composite coating with high ductility, the target is microfiber base cloth, non-woven cloth, woven cloth or knitted cloth.
The invention also provides an application of the high-ductility aqueous polyurethane composite coating prepared by the method, which is used for preparing superfine fiber PU synthetic leather, and the target for coating is superfine fiber base cloth;
the tensile load of the superfine fiber PU synthetic leather is more than or equal to 540N, and the elongation at break is more than or equal to 60 percent.
The mechanism of the invention is as follows:
The polyurethane is polymerized by adding an active hydrogen substance (such as an oligomer dihydric alcohol) of an oligomer and an active hydrogen substance (such as ethylene glycol) of a small molecule simultaneously, wherein the active hydrogen end group of the active hydrogen substance reacts with diisocyanate to form a polyurethane molecular chain, the active hydrogen substance of the oligomer forms a soft segment of the polyurethane, the active hydrogen substance of the small molecule forms a hard segment of the polyurethane, the soft segment provides flexibility of the molecular chain and the hard segment provides rigidity of the molecular chain, the higher the content of the hard segment is, the higher the rigidity and the lower the flexibility of the material are, and the rigidity of the material is generally evaluated at a 100% modulus level, so that the ratio of the hard segment of the polyurethane is evaluated. The high 100% modulus aqueous polyurethane resin is polyurethane with high hard segment content, and the low 100% modulus aqueous polyurethane resin is polyurethane with high soft segment content.
By analyzing the precipitation behavior of small molecules in polyurethane matrix containing different soft segment ratios, it is believed that the soft segment ratio affects the solubility of small molecule additives in the polymer matrix. Polyurethane with a large soft segment ratio can dissolve more small molecule lubricant. The polyurethane with high soft segment ratio has better ductility, and no extra small molecular lubricant is generally needed to be added for toughening modification, but the polyurethane with high soft segment ratio has too low strength to be used for coating of synthetic leather, and the polyurethane with high soft segment ratio needs strength modification instead of toughening modification, so that the problem faced by the prior art cannot be solved even though the polyurethane with high small molecular auxiliary agent solubility. The aqueous polyurethane with high hard segment content, which has more hard segments and less soft segments, has high strength, but has insufficient ductility, and is generally improved by adding small molecular auxiliary agents.
In the early stage of development, the aqueous polyurethane with the 100% modulus of 44MPa and the same aqueous polyurethane with the 100% modulus of 1.5MPa are compounded to adjust the aqueous polyurethane with different 100% modulus levels, namely the aqueous polyurethane with different soft segment contents, so as to adjust the strength and the ductility of the coating. To ensure the desired strength, the 100% modulus of the aqueous polyurethane resin is adjusted to at least more than 30MPa, and the addition of the small molecular lubricant can improve ductility, but the improvement level is limited because an oil film is generated when the small molecular lubricant is added to 12 parts or more (i.e., the addition amount of the small molecular lubricant is 12wt% or more of the aqueous polyurethane), and the 100% modulus is 30MPa.
The hard segment has poor compatibility with the small molecular lubricant, and the small molecular lubricant has different ultimate precipitation concentrations in polyurethane with different hard segment contents, wherein the ultimate precipitation concentrations are the addition proportion of the small molecular lubricant when oil spots or precipitates appear on the surface of the polyurethane film when the small molecular lubricant with different proportions is added into the aqueous polyurethane, then the film is scraped into a film, and the film is cooled to 25 ℃ after being dried at 100 ℃. When we set a low 100% modulus aqueous polyurethane resin containing a higher concentration of small molecular lubricant distribution on top of and below a high 100% modulus aqueous polyurethane resin containing a small molecular lubricant distribution near the ultimate precipitation concentration, it was found that the high concentration of small molecular lubricant in the low 100% modulus aqueous polyurethane resin diffused into the high 100% modulus aqueous polyurethane resin, resulting in a significant increase in ductility of the material as a whole. When the small molecular lubricant exceeds the limit concentration, larger outward diffusion power is generated, and the difference of the lubricant concentration at two sides causes the small molecular lubricant to generate inward diffusion power.
The condition that the small molecular lubricant has power of inward diffusion is that the content of the small molecular lubricant in the upper layer aqueous polyurethane coating and the content of the small molecular lubricant in the lower layer aqueous polyurethane coating are respectively more than or equal to 1.5 times of the content of the small molecular lubricant in the middle layer aqueous polyurethane coating.
In the preparation process, the concentration of the small molecular lubricant in the upper layer, the middle layer and the lower layer does not exceed the limit precipitation concentration, the concentration of the small molecular lubricant in the middle layer aqueous polyurethane coating is 8-10 parts, and the concentration is close to the limit concentration. After 48 hours of treatment at a high temperature of 50-70 ℃, the small molecular lubricant in the upper layer and the lower layer diffuses to the middle layer, and the actual small molecular lubricant concentration in the middle layer aqueous polyurethane coating exceeds the limit concentration.
In the invention, the polyurethanes in the upper, middle and lower aqueous polyurethane coatings are ensured to be the same materials, and the high 100% modulus aqueous polyurethane resin and the low 100% modulus aqueous polyurethane resin have the same monomer units and are different only in soft segment content. The upper layer material is replaced by a coating of other materials with the same solubility, and the existence of concentration difference causes precipitation of small molecular lubricant at the interface due to poor compatibility of the two materials, so that material layering is aggravated.
Advantageous effects
(1) According to the preparation method of the aqueous polyurethane composite coating with high ductility, the low 100% modulus aqueous polyurethane resin containing the small molecular lubricant distribution with higher concentration is arranged above and below the high 100% modulus aqueous polyurethane resin containing the small molecular lubricant distribution with the concentration close to the limit precipitation concentration, and the small molecular lubricant exceeding the limit concentration can stably exist in the high 100% modulus aqueous polyurethane resin by utilizing diffusion power, so that the material with high strength and high ductility is obtained.
(2) The high-ductility aqueous polyurethane composite coating is used for preparing superfine fiber PU synthetic leather, and has excellent strength and toughness.
Drawings
FIG. 1 is a schematic illustration of a high ductility aqueous polyurethane composite coating of the present invention;
FIG. 2 spectrum of differences before and after heat treatment at 50℃for 48 hours in example 1;
Wherein, the coating is 1-upper layer aqueous polyurethane coating, 2-middle layer aqueous polyurethane coating and 3-lower layer aqueous polyurethane coating.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The test method related by the invention comprises the following steps:
100% modulus the tensile force at which the film stretches to 100% elongation at break was measured using a universal tester and then divided by the cross-sectional area of the film before stretching, which is the 100% modulus of the material.
The tensile strength and elongation at break of the composite coating are measured by a universal tester according to GB/T1040.3-2006, wherein the distance between the standard lines of the samples is 100mm, and the test speed is 200 mm/min+/-10 mm/min.
The tensile load and the breaking elongation of the synthetic leather are measured according to QBT 4909-2016 aqueous polyurethane superfine fiber synthetic leather.
The aqueous polyurethane resin is anionic aqueous polyurethane resin, the low-modulus aqueous polyurethane resin and the high-modulus aqueous polyurethane resin are different in the ratio of soft segment parts, the soft segment of the low-modulus aqueous polyurethane resin (namely the third part in the structural formula) is 40 times of the soft segment of the high-modulus aqueous polyurethane resin, and the two aqueous polyurethane resins are respectively:
the structural formula of the high 100% modulus aqueous polyurethane resin with the 100% modulus of 44MPa is as follows:
The low 100% modulus aqueous polyurethane resin with 100% modulus of 1.0MPa has the structural formula:
the number average molecular weight of the high modulus aqueous polyurethane resin was measured to be 15.6 ten thousand, and the number average molecular weight of the low modulus aqueous polyurethane resin was measured to be 16.8 ten thousand. The aqueous polyurethane resin with different moduli can be prepared by blending aqueous polyurethane resin with high 100% modulus and aqueous polyurethane resin with low 100% modulus. In the specific examples and comparative examples, the blending ratio is:
The aqueous polyurethane resin with 100% modulus of 1.2MPa and the aqueous polyurethane resin with 100% modulus of 1.0MPa, wherein the mass ratio of the aqueous polyurethane resin to the aqueous polyurethane resin is 99.5:0.5, and the aqueous polyurethane resin with 100% modulus of 44MPa are dispersed in water and uniformly mixed.
The aqueous polyurethane resin with 100% modulus of 1.3MPa and the aqueous polyurethane resin with 100% modulus of 1.0MPa, wherein the mass ratio of the aqueous polyurethane resin to the aqueous polyurethane resin is 99.30:0.70, and the aqueous polyurethane resin with 100% modulus of 44MPa are dispersed in water and uniformly mixed.
The 100% aqueous polyurethane with the modulus of 1.5MPa is obtained by uniformly dispersing the 100% aqueous polyurethane resin with the modulus of 1.0MPa and the 100% aqueous polyurethane with the modulus of 44MPa in water according to the mass ratio of 98.84:1.16.
The 100% aqueous polyurethane with the modulus of 1.6MPa is obtained by uniformly dispersing the 100% aqueous polyurethane resin with the modulus of 1.0MPa and the 100% aqueous polyurethane with the modulus of 44MPa in water according to the mass ratio of 98.60:1.40.
The 100% aqueous polyurethane with the modulus of 1.8MPa is obtained by uniformly dispersing the 100% aqueous polyurethane resin with the modulus of 1.0MPa and the 100% aqueous polyurethane with the modulus of 44MPa in water according to the mass ratio of 98.14:1.86.
The aqueous polyurethane resin with 100% modulus of 2.0MPa and the aqueous polyurethane with 100% modulus of 44MPa are uniformly mixed in water, wherein the mass ratio of the aqueous polyurethane resin with 100% modulus of 1.0MPa is 97.67:2.33.
The aqueous polyurethane with the 100% modulus of 34MPa is obtained by uniformly dispersing aqueous polyurethane resin with the 100% modulus of 1.0MPa and aqueous polyurethane with the 100% modulus of 44MPa in water according to the mass ratio of 23.26:76.74.
The 100% aqueous polyurethane with the modulus of 35MPa is obtained by uniformly dispersing aqueous polyurethane resin with the modulus of 100% of 1.0MPa and aqueous polyurethane with the modulus of 100% of 44MPa in water according to the mass ratio of 20.93:79.07.
The 100% aqueous polyurethane with the modulus of 36MPa is obtained by uniformly dispersing aqueous polyurethane resin with the modulus of 1.0MPa and aqueous polyurethane with the modulus of 44MPa in water, wherein the mass ratio of the aqueous polyurethane resin to the aqueous polyurethane is 18.60:81.40.
The aqueous polyurethane resin with 100% modulus of 40MPa and the aqueous polyurethane resin with 100% modulus of 1.0MPa, which are in mass ratio of 9.30:90.70, are dispersed in water and uniformly mixed.
The microfiber base cloth used in the examples was manufactured by Toray Industries, incA series of 500R products;
the non-woven fabric used in the example is non-woven fabric with the thickness of 1.2 mm of the Yanrui non-woven product Limited company in the conventional market, and the product number is leather base cloth-07;
the woven cloth used in the embodiment is terylene woven cloth of Dongguan city collection textile Co., ltd, and the product number is B103/8P4736;
the knitted fabric used in the examples was a polyester knitted fabric having a gram weight of 220g/m 2, product number XX, from Tung xiang brocade fabric Lei knitting Co., ltd.
TABLE 1 precipitation limit addition amount of small molecular lubricants with different 100% moduli
| 100% Modulus | Precipitation limit of small molecule lubricant | Remarks |
| 40MPa | 9 Parts (relative to 100 parts polyurethane) | At 9 parts a slight oil spot started to appear |
| 35MPa | 10 Parts (relative to 100 parts polyurethane) | A slight oil stain started to appear at 10 parts |
| 30MPa | 12 Parts (relative to 100 parts polyurethane) | A slight oil stain started to appear at 12 parts |
| 2MPa | More than 30 parts (relative to 100 parts of polyurethane) | Adding 30 parts of the additive without oil spots |
| 1MPa | More than 30 parts (relative to 100 parts of polyurethane) | Adding 30 parts of the additive without oil spots |
The term "precipitation limit" in table 1 refers to the minimum addition ratio of the small molecular lubricant when oil spots or precipitates appear on the surface of the aqueous polyurethane coating by adjusting the addition ratio of the small molecular lubricant in the aqueous polyurethane, and cooling to 25 ℃ after drying at 100 ℃.
Example 1
A preparation method of a high-ductility aqueous polyurethane composite coating is shown in figure 1, and comprises the following specific steps:
(1) The preparation method comprises the steps of carrying out roller coating treatment on the surface of a microfiber base fabric, and drying for 60min at 80 ℃ to form a lower-layer aqueous polyurethane coating 3 with the thickness of 17 mu m, wherein the lower-layer aqueous polyurethane coating comprises 100 parts of low-100% modulus aqueous polyurethane resin, 15 parts of triethyl phosphate and 500 parts of water in parts by weight, wherein the 100% modulus of the low-100% modulus aqueous polyurethane resin is 2MPa;
(2) The middle-layer aqueous polyurethane slurry is roll-coated on the lower-layer aqueous polyurethane coating 3, and is dried for 60min at 80 ℃ to be solidified into the middle-layer aqueous polyurethane coating 2 with the thickness of 83 mu m, wherein the middle-layer aqueous polyurethane slurry comprises 100 parts of high 100% modulus aqueous polyurethane resin, 10 parts of triethyl phosphate and 500 parts of water in parts by weight, and the 100% modulus of the high 100% modulus aqueous polyurethane resin is 34MPa;
(3) The upper layer aqueous polyurethane slurry is subjected to roller coating treatment on the middle layer aqueous polyurethane coating 2, is dried at 80 ℃ for 60min and solidified to form an upper layer aqueous polyurethane coating 1 with the same thickness as the lower layer aqueous polyurethane coating 3, and is then subjected to standing at 70 ℃ for 60h to obtain the aqueous polyurethane composite coating with high ductility, wherein the upper layer aqueous polyurethane slurry comprises, by mass, 100 parts of low 100% modulus aqueous polyurethane resin, 15 parts of triethyl phosphate and 500 parts of water, and the 100% modulus of the low 100% modulus aqueous polyurethane resin is 2MPa.
The prepared high-ductility aqueous polyurethane composite coating has tensile strength of 149N, elongation at break of 324 percent, and the superfine fiber PU synthetic leather has tensile load of 540N and elongation at break of 89 percent.
The concentration change and the ductility change of the triethyl phosphate on the upper and lower surfaces are measured by taking the aqueous polyurethane composite coating with high ductility as a measurement sample, and as shown in fig. 2, the characteristic peak intensity of the 1280cm -1 phosphate group is found to be obviously changed, the characteristic peak intensity shows a tendency of reduction after heat treatment, the surface of the composite material has no precipitation phenomenon, the elongation after the heat treatment is increased by 1.24 times compared with that before the heat treatment (261%), and the triethyl phosphate in the upper and lower layers is presumed to be diffused to the middle layer.
Comparative example 1
A preparation method of a water-based polyurethane composite coating is basically the same as that of the example 1, except that the addition amounts of the triethyl phosphate in the upper, middle and lower layers are respectively 12, 10 and 12 parts by mass (namely, the mass parts of the triethyl phosphate in the upper and lower water-based polyurethane coatings are smaller than 1.5 times of that of the middle water-based polyurethane coating).
The tensile strength of the prepared aqueous polyurethane composite coating is 153N, the elongation at break is 268%, the aqueous polyurethane composite coating is used for preparing superfine fiber PU synthetic leather, the tensile load of the superfine fiber PU synthetic leather is 549N, and the elongation at break is 58%.
Comparing comparative example 1 with example 1, it can be found that the elongation at break of the aqueous polyurethane composite coating of comparative example 1 and the produced ultrafine fiber PU synthetic leather is significantly lower than that of example 1, because the interlayer concentration difference of the small molecular lubricant in comparative example 1 does not promote in-diffusion.
Example 2
The preparation method of the high-ductility aqueous polyurethane composite coating comprises the following specific steps:
(1) The preparation method comprises the steps of carrying out roller coating treatment on the surface of microfiber base cloth, and drying for 60min at 80 ℃ to form a lower-layer aqueous polyurethane coating with the thickness of 10 mu m, wherein the lower-layer aqueous polyurethane coating comprises 100 parts of low-100% modulus aqueous polyurethane resin (namely aqueous polyurethane with high soft segment content), 14 parts of triethyl phosphate and 70 parts of water in parts by weight, and the 100% modulus of the low-100% modulus aqueous polyurethane resin is 1.5MPa;
(2) The middle-layer aqueous polyurethane slurry is subjected to roller coating treatment on the lower-layer aqueous polyurethane coating, and is dried for 60min at 80 ℃ to be solidified to form the middle-layer aqueous polyurethane coating with the thickness of 90 mu m, wherein the middle-layer aqueous polyurethane slurry comprises 100 parts of high 100% modulus aqueous polyurethane resin (namely, high hard segment content aqueous polyurethane), 8 parts of triethyl phosphate and 70 parts of water in parts by weight, and the 100% modulus of the high 100% modulus aqueous polyurethane resin is 40MPa;
(3) The upper-layer aqueous polyurethane slurry is subjected to roller coating treatment on the middle-layer aqueous polyurethane coating, is dried at 80 ℃ for 60min and is solidified to form an upper-layer aqueous polyurethane coating with the same thickness as the lower-layer aqueous polyurethane coating, and is then subjected to standing for 48h at 50 ℃ to obtain the aqueous polyurethane composite coating with high ductility, wherein the upper-layer aqueous polyurethane slurry comprises, by mass, 100 parts of low 100% modulus aqueous polyurethane resin, 14 parts of triethyl phosphate and 70 parts of water, and the 100% modulus of the low 100% modulus aqueous polyurethane resin is 1MPa.
The prepared high-ductility aqueous polyurethane composite coating has a tensile strength of 207N, an elongation at break of 255%, and a tensile load of 621N and an elongation at break of 60% of the superfine fiber PU synthetic leather.
Example 3
The preparation method of the high-ductility aqueous polyurethane composite coating comprises the following specific steps:
(1) The preparation method comprises the steps of carrying out roller coating treatment on the surface of a microfiber base fabric, and drying for 60min at 80 ℃ to form a lower-layer aqueous polyurethane coating with the thickness of 12 mu m, wherein the lower-layer aqueous polyurethane coating comprises 100 parts of low-100% modulus aqueous polyurethane resin (namely aqueous polyurethane with high soft segment content), 15 parts of triethyl phosphate and 250 parts of water in parts by weight, wherein the 100% modulus of the low-100% modulus aqueous polyurethane resin is 1MPa;
(2) The middle-layer aqueous polyurethane slurry is subjected to roller coating treatment on the lower-layer aqueous polyurethane coating, and is dried for 60min at 80 ℃ to be solidified to form the middle-layer aqueous polyurethane coating with the thickness of 100 mu m, wherein the middle-layer aqueous polyurethane slurry comprises 100 parts of high 100% modulus aqueous polyurethane resin (namely, high hard segment content aqueous polyurethane), 9 parts of triethyl phosphate and 250 parts of water in parts by weight, and the 100% modulus of the high 100% modulus aqueous polyurethane resin is 35MPa;
(3) The upper-layer aqueous polyurethane slurry is subjected to roller coating treatment on the middle-layer aqueous polyurethane coating, is dried at 80 ℃ for 60min and is solidified to form an upper-layer aqueous polyurethane coating with the same thickness as the lower-layer aqueous polyurethane coating, and is then subjected to standing for 50h at 60 ℃ to obtain the aqueous polyurethane composite coating with high ductility, wherein the upper-layer aqueous polyurethane slurry comprises, by mass, 100 parts of low 100% modulus aqueous polyurethane resin, 15 parts of triethyl phosphate and 250 parts of water, and the 100% modulus of the low 100% modulus aqueous polyurethane resin is 1.5MPa.
The prepared high-ductility aqueous polyurethane composite coating has the tensile strength of 191N, the elongation at break of 298%, the tensile load of 601N and the elongation at break of 76%.
Example 4
The preparation method of the high-ductility aqueous polyurethane composite coating comprises the following specific steps:
(1) The preparation method comprises the steps of carrying out roller coating treatment on the surface of a non-woven fabric, and drying for 60min at 80 ℃ to form a lower aqueous polyurethane coating with the thickness of 20 mu m, wherein the lower aqueous polyurethane coating comprises 100 parts of low 100% modulus aqueous polyurethane resin (namely aqueous polyurethane with high soft segment content), 16 parts of triethyl phosphate and 100 parts of water in parts by weight, and the 100% modulus of the low 100% modulus aqueous polyurethane resin is 1.6MPa;
(2) The middle-layer aqueous polyurethane slurry is subjected to roller coating treatment on the lower-layer aqueous polyurethane coating, and is dried for 60min at 80 ℃ to be solidified to form the middle-layer aqueous polyurethane coating with the thickness of 200 mu m, wherein the middle-layer aqueous polyurethane slurry comprises 100 parts of high 100% modulus aqueous polyurethane resin (namely, high hard segment content aqueous polyurethane), 8.5 parts of triethyl phosphate and 80 parts of water in parts by weight, and the 100% modulus of the high 100% modulus aqueous polyurethane resin is 36MPa;
(3) The upper layer aqueous polyurethane slurry is subjected to roller coating treatment on the middle layer aqueous polyurethane coating, is dried at 80 ℃ for 60min and is solidified to form an upper layer aqueous polyurethane coating with the same thickness as the lower layer aqueous polyurethane coating, and is then subjected to standing at 55 ℃ for 52h to obtain the aqueous polyurethane composite coating with high ductility, wherein the upper layer aqueous polyurethane slurry comprises, by mass, 100 parts of low 100% modulus aqueous polyurethane resin, 14 parts of triethyl phosphate and 100 parts of water, and the 100% modulus of the low 100% modulus aqueous polyurethane resin is 1.2MPa.
The tensile strength of the prepared high-ductility aqueous polyurethane composite coating is 184N, and the elongation at break is 377%.
Example 5
The preparation method of the high-ductility aqueous polyurethane composite coating comprises the following specific steps:
(1) The method comprises the steps of carrying out roller coating treatment on the surface of a woven fabric, and drying for 60min at 80 ℃ to form a lower aqueous polyurethane coating with the thickness of 25 mu m, wherein the lower aqueous polyurethane coating comprises 100 parts of low 100% modulus aqueous polyurethane resin (namely aqueous polyurethane with high soft segment content), 18 parts of triethyl phosphate and 200 parts of water in parts by weight, and the 100% modulus of the low 100% modulus aqueous polyurethane resin is 1.3MPa;
(2) The middle-layer aqueous polyurethane slurry is subjected to roller coating treatment on the lower-layer aqueous polyurethane coating, and is dried for 60min at 80 ℃ to be solidified to form the middle-layer aqueous polyurethane coating with the thickness of 250 mu m, wherein the middle-layer aqueous polyurethane slurry comprises 100 parts of high 100% modulus aqueous polyurethane resin (namely, high hard segment content aqueous polyurethane), 8.5 parts of triethyl phosphate and 180 parts of water in parts by weight, and the 100% modulus of the high 100% modulus aqueous polyurethane resin is 36MPa;
(3) The upper-layer aqueous polyurethane slurry is subjected to roller coating treatment on the middle-layer aqueous polyurethane coating, is dried at 80 ℃ for 60min and is solidified to form an upper-layer aqueous polyurethane coating with the same thickness as the lower-layer aqueous polyurethane coating, and is then subjected to standing for 54h at 65 ℃ to obtain the aqueous polyurethane composite coating with high ductility, wherein the upper-layer aqueous polyurethane slurry comprises, by mass, 100 parts of low 100% modulus aqueous polyurethane resin, 16 parts of triethyl phosphate and 200 parts of water, and the 100% modulus of the low 100% modulus aqueous polyurethane resin is 1.6MPa.
The tensile strength of the prepared high-ductility aqueous polyurethane composite coating is 201N, and the elongation at break is 398%.
Example 6
The preparation method of the high-ductility aqueous polyurethane composite coating comprises the following specific steps:
(1) The lower-layer aqueous polyurethane slurry is subjected to roller coating treatment on the surface of the knitted fabric, and is dried for 60min at 80 ℃ to be solidified to form a lower-layer aqueous polyurethane coating with the thickness of 50 mu m, wherein the lower-layer aqueous polyurethane slurry comprises 100 parts of low-100% modulus aqueous polyurethane resin (namely aqueous polyurethane with high soft segment content), 20 parts of triethyl phosphate and 300 parts of water in parts by weight, and the 100% modulus of the low-100% modulus aqueous polyurethane resin is 1.8MPa;
(2) The middle-layer aqueous polyurethane slurry is subjected to roller coating treatment on the lower-layer aqueous polyurethane coating, and is dried for 60min at 80 ℃ to be solidified to form the middle-layer aqueous polyurethane coating with the thickness of 300 mu m, wherein the middle-layer aqueous polyurethane slurry comprises 100 parts of high 100% modulus aqueous polyurethane resin (namely, high hard segment content aqueous polyurethane), 10 parts of triethyl phosphate and 280 parts of water in parts by weight, and the 100% modulus of the high 100% modulus aqueous polyurethane resin is 34MPa;
(3) The upper layer aqueous polyurethane slurry is subjected to roller coating treatment on the middle layer aqueous polyurethane coating, is dried at 80 ℃ for 60min and is solidified to form an upper layer aqueous polyurethane coating with the same thickness as the lower layer aqueous polyurethane coating, and is then subjected to standing for 55h at 70 ℃ to obtain the aqueous polyurethane composite coating with high ductility, wherein the upper layer aqueous polyurethane slurry comprises, by mass, 100 parts of low 100% modulus aqueous polyurethane resin, 18 parts of triethyl phosphate and 300 parts of water, and the 100% modulus of the low 100% modulus aqueous polyurethane resin is 1.8MPa.
The tensile strength of the prepared high-ductility aqueous polyurethane composite coating is 209N, and the elongation at break is 412%.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311002985.7A CN117005213B (en) | 2023-08-09 | 2023-08-09 | Preparation and application of a waterborne polyurethane composite coating with high ductility |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311002985.7A CN117005213B (en) | 2023-08-09 | 2023-08-09 | Preparation and application of a waterborne polyurethane composite coating with high ductility |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117005213A CN117005213A (en) | 2023-11-07 |
| CN117005213B true CN117005213B (en) | 2025-07-15 |
Family
ID=88574113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311002985.7A Active CN117005213B (en) | 2023-08-09 | 2023-08-09 | Preparation and application of a waterborne polyurethane composite coating with high ductility |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117005213B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118127837B (en) * | 2024-04-03 | 2026-02-10 | 北京服装学院 | A composite fabric with high hardness, high elasticity, and a wide range of hardness variation, and its preparation method. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1420497A (en) * | 1972-03-23 | 1976-01-07 | Kufner Textilwerke Kg | Heat-sealable adhesive inserts for fabrics |
| CN112266717A (en) * | 2020-10-26 | 2021-01-26 | 中国科学院兰州化学物理研究所 | Preparation of silicon-oil-containing lubricating anticorrosive composite coating with low friction coefficient |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4204177B2 (en) * | 2000-06-13 | 2009-01-07 | 大日精化工業株式会社 | Thermal recording material |
| TW201404793A (en) * | 2012-07-17 | 2014-02-01 | Megaology Chemical Co Ltd | Aqueous polyurethane dispersion solution and preparation method |
| WO2017040109A1 (en) * | 2015-09-02 | 2017-03-09 | Icl-Ip America Inc. | Polyurethane solution and use thereof |
-
2023
- 2023-08-09 CN CN202311002985.7A patent/CN117005213B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1420497A (en) * | 1972-03-23 | 1976-01-07 | Kufner Textilwerke Kg | Heat-sealable adhesive inserts for fabrics |
| CN112266717A (en) * | 2020-10-26 | 2021-01-26 | 中国科学院兰州化学物理研究所 | Preparation of silicon-oil-containing lubricating anticorrosive composite coating with low friction coefficient |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117005213A (en) | 2023-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117005213B (en) | Preparation and application of a waterborne polyurethane composite coating with high ductility | |
| CN110230117B (en) | Method for improving strength and strain of polyurethane fiber | |
| CN106366651B (en) | A kind of low temperature resistant flame retardant nylon cable tie material and preparation method thereof | |
| CN101265620B (en) | Blending fire retardant -type terylene industrial filament and its manufacturing technique | |
| DE112017008368B4 (en) | Process for producing elastic polyurethane fiber | |
| CN105019052B (en) | A kind of preparation method of high performance polyurethane elastomer | |
| CN118186607A (en) | Cutting-resistant ultra-high molecular weight polyethylene fiber and preparation method and application thereof | |
| CN117721555B (en) | Terylene FDY (fully drawn yarn) oiling agent and preparation method thereof | |
| JP2019515152A (en) | Porous, ultra-soft, ultra-fine polyester fiber and method for producing the same | |
| CN107460559A (en) | A kind of preparation method of graphene polyester fiber | |
| CN111021070A (en) | A kind of multi-layer fabric with polyurethane coating and preparation method thereof | |
| CN1124313C (en) | Polyurethane and elastane that are finished to impart antistatic properties | |
| CN114737388A (en) | Waterproof polyethylene yarn and preparation method thereof | |
| CN117926433A (en) | Cut-resistant fiber and preparation method thereof | |
| TW201714958A (en) | Masterbatch for abrasion resistant fiber and method of preparing the same and abrasion resistant fiber prepared by using the same | |
| CN110373022B (en) | Modified nylon composite material, preparation method and application thereof | |
| CN110922575A (en) | Colored conductive polyester fiber and preparation method thereof | |
| CN115787133A (en) | A supersoft reinforced flat sea-island fiber and its preparation method | |
| JP3265714B2 (en) | High toughness black raw polyamide fiber | |
| US11905628B2 (en) | Cut resistant fabric | |
| CN115467042B (en) | PBT stretch fiber yarn with high scratch resistance and preparation method thereof | |
| CN114456509B (en) | Modified polyolefin for low-melting-point carbon black master batch and preparation method thereof | |
| CN107541802A (en) | Short fibre of soft, wear-resistant and its production and use | |
| TW201823535A (en) | Abrasion resistant fiber, abrasion and impact resistant fiber and masterbatches thereof | |
| CN112442753A (en) | Preparation method of novel anti-cutting material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |