CN114673014B - Weakening-free PU instrument board leather and preparation method thereof, and instrument board - Google Patents
Weakening-free PU instrument board leather and preparation method thereof, and instrument board Download PDFInfo
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- CN114673014B CN114673014B CN202210317292.6A CN202210317292A CN114673014B CN 114673014 B CN114673014 B CN 114673014B CN 202210317292 A CN202210317292 A CN 202210317292A CN 114673014 B CN114673014 B CN 114673014B
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- 239000010985 leather Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000004814 polyurethane Substances 0.000 claims abstract description 163
- 229920002635 polyurethane Polymers 0.000 claims abstract description 151
- 239000010410 layer Substances 0.000 claims abstract description 86
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 71
- 239000004744 fabric Substances 0.000 claims abstract description 65
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 claims abstract description 45
- 239000012948 isocyanate Substances 0.000 claims abstract description 44
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 44
- 239000002344 surface layer Substances 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 32
- 229920005862 polyol Polymers 0.000 claims abstract description 25
- 150000003077 polyols Chemical class 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 60
- 239000004359 castor oil Substances 0.000 claims description 26
- 235000019438 castor oil Nutrition 0.000 claims description 26
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 26
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 24
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 claims description 23
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 22
- 239000004254 Ammonium phosphate Substances 0.000 claims description 22
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 22
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 22
- 239000003063 flame retardant Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 150000005846 sugar alcohols Polymers 0.000 claims description 13
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical group C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002649 leather substitute Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- 239000000463 material Substances 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- 230000008569 process Effects 0.000 description 11
- 239000003431 cross linking reagent Substances 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 9
- 239000011527 polyurethane coating Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 229910007991 Si-N Inorganic materials 0.000 description 8
- 229910006294 Si—N Inorganic materials 0.000 description 8
- 230000009471 action Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013530 defoamer Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000003313 weakening effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 210000003491 skin Anatomy 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- -1 acrylic ester Chemical class 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
-
- 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
- D06N2211/26—Vehicles, transportation
- D06N2211/261—Body finishing, e.g. headliners
-
- 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 application relates to the field of polyurethane synthetic leather, and particularly discloses weakening-free PU instrument board leather, a preparation method thereof and an instrument board. The weakening-free PU instrument board leather comprises a polyurethane surface layer, a solvent-free polyurethane adhesive layer and a base cloth layer. The preparation method of the weakening-free PU instrument board leather comprises the following steps: dissolving polyurethane resin in a solvent, coating the solvent on release paper, and heating and drying to obtain a polyurethane surface layer; mixing polyol, isocyanate, a catalyst and a curing agent, coating the mixture on the polyurethane surface layer, and heating to form a solvent-free polyurethane adhesive layer; and attaching a base cloth on the solvent-free polyurethane adhesive layer to form a base cloth layer. And the instrument board is coated with the weakening-free PU instrument board leather. The polyurethane part and the base cloth part of the weakening-free PU instrument board leather obtained by the application have good bonding property; according to the application, the solvent-free polyurethane adhesive layer is introduced, so that the bonding fastness between the polyurethane part and the base cloth in the PU instrument board leather is improved.
Description
Technical Field
The application relates to the field of polyurethane synthetic leather, in particular to weakening-free PU instrument board leather, a preparation method thereof and an instrument board.
Background
With the development of social economy and the improvement of living standard of people, automobiles become one of the important tools frequently used by people; the instrument panel of an automobile is increasingly used as an assembly for installing various indicators and ignition switches in the cab of the automobile.
In order to ensure that at critical moments, the airbag can burst out of the instrument panel; the skin covered on the instrument panel is usually weakened by a laser. However, obvious marks appear on the surface of the weakened instrument panel skin, thereby reducing the grade of the whole vehicle. At present, the weakening-free skin is increasingly applied to the instrument panel of the automobile, and the skin does not need to be weakened, so that the problem of appearance defects after weakening is solved.
The polyvinyl chloride (PVC) material is relatively simple in extrusion lamination, convenient to operate, firm in combination of PVC and base cloth, not easy to peel and good in durability; so most of the weakening-free epidermis adopts PVC leather at present. However, the environmental protection problem of PVC leather always has the problem that the grade sense can not be improved. Polyurethane (PU) has better environmental protection property, and the polyurethane is applied to instrument board leather, thereby being beneficial to improving the environmental protection property. The inventors found that: the existing weakening-free PU instrument board leather has the problems that the combination property of a polyurethane part and a base cloth part is poor and the polyurethane part and the base cloth part are easy to peel off, so that the durability of the instrument board leather is reduced.
Disclosure of Invention
The application provides weakening-free PU instrument board leather, a preparation method thereof and an instrument board in order to improve the combination fastness of polyurethane parts and base cloth in the weakening-free PU instrument board leather.
In a first aspect, a weakening-free PU instrument board leather is provided, and the following technical scheme is adopted:
The weakening-free PU instrument board leather comprises a polyurethane surface layer, a solvent-free polyurethane adhesive layer and a base cloth layer;
The solvent-free polyurethane forming the solvent-free polyurethane adhesive layer is prepared from the following raw materials in parts by weight: 95-105 parts of polyol, 48-70 parts of isocyanate, 0.04-0.06 part of catalyst and 0.18-0.3 part of curing agent.
By adopting the technical scheme, as the solvent-free polyurethane is an anhydrous solvent-free system, no gas is generated when the solvent-free polyurethane is attached to the base cloth; therefore, the solvent-free polyurethane and the base cloth can be more tightly attached, so that the combination property between the solvent-free polyurethane and the base cloth is improved; furthermore, the connection of the solvent-free polyurethane adhesive layer avoids weakening the combination fastness between the polyurethane part and the base cloth in the PU instrument board leather and greatly improves.
In a specific embodiment, the solvent-free polyurethane is prepared by mixing and heating group A materials and group B materials;
The group A raw materials comprise polyalcohol, and the group B raw materials comprise isocyanate, catalyst and curing agent.
In a specific embodiment, the group A raw material further comprises 35-50 parts by mass of an ammonium phosphate flame retardant.
By adopting the technical scheme, the ammonium phosphate flame retardant has no obvious influence on the bonding fastness of the polyurethane part and the base cloth part in the PU instrument board leather without weakening while endowing the solvent-free polyurethane with flame retardance.
In a specific embodiment, the group a feedstock further comprises 0.15 to 0.25 parts by mass of a silicone leveling agent.
By adopting the technical scheme, the organic silicon leveling agent increases the coating property of the solvent-free polyurethane raw material, and has positive significance for improving the bonding fastness of the polyurethane part and the base cloth part in the obtained instrument board leather.
In a specific embodiment, the group B material further comprises 5 to 10 parts by mass of castor oil and 6 to 12 parts by mass of tetramethyldisilazane.
By adopting the technical scheme, on one hand, the hydroxyl energy of castor oil reacts with isocyanate, and on the other hand, unsaturated double bond energy of castor oil reacts with tetramethyl disilazane in a hydrosilylation reaction, so that the tetramethyl disilazane with Si-N bond is firmly connected in the molecular structure of solvent-free polyurethane through the bridge action of the castor oil; because the Si-N bond has stronger polarity and can react with the base cloth to form a covalent bond, the solvent-free polyurethane adhesive layer and the base cloth layer are firmly combined together through valence bond connection, and the polyurethane part in the instrument panel leather and the base cloth are firmly combined.
In a specific embodiment, the polyisocyanate is toluene diisocyanate; the polyol is a polyether polyol.
By adopting the technical scheme, the types of polyisocyanate and polyol are optimized, and the solvent-free polyurethane with good performance is obtained.
In a specific embodiment, the catalyst is a metallic bismuth based catalyst and the curing agent is dibenzylamine.
By adopting the technical scheme, the metal bismuth catalyst and the dibenzyl amine are favorable for successfully obtaining the solvent-free polyurethane with ideal performance.
In a specific embodiment, the decorative board further comprises an aqueous decorative layer, and the material of the aqueous decorative layer is aqueous polyacrylate.
In a second aspect, a preparation method of weakening-free PU instrument board leather is provided, and the following technical scheme is adopted:
The preparation method of the weakening-free PU instrument board leather comprises the following steps:
dissolving polyurethane resin in a solvent, coating the solvent on release paper, and heating and drying to obtain a polyurethane surface layer;
taking polyol, isocyanate, a catalyst and a curing agent according to a formula, mixing, coating on the polyurethane surface layer, and heating to 90-135 ℃ to form a solvent-free polyurethane adhesive layer;
And attaching a base cloth on the solvent-free polyurethane adhesive layer to form a base cloth layer.
By adopting the technical scheme, the weakening-free PU instrument board leather is smoothly manufactured.
In a third aspect, an instrument panel is provided, which adopts the following technical scheme:
and the instrument board is coated with the weakening-free PU instrument board leather.
Through adopting above-mentioned technical scheme, polyurethane part and the laminating of basic cloth part are inseparable in the weakening-free PU instrument board leather of instrument board, and weakening-free PU instrument board leather smell is little, more environmental protection.
In summary, the present application has at least one of the following advantages:
1. the polyurethane part and the base cloth part of the weakening-free PU instrument board leather obtained by the application have good combination, and the stripping force between the polyurethane part and the base cloth part is high and even can not be stripped.
2. According to the application, the solvent-free polyurethane adhesive layer is introduced, and the solvent-free polyurethane adhesive layer can be tightly attached to the base cloth by utilizing the characteristic of no water and no solvent of the solvent-free polyurethane; and the bonding fastness between the polyurethane part and the base cloth in the PU instrument board leather without weakening is improved through the connection of the solvent-free polyurethane bonding layer.
3. In the application, castor oil and tetramethyl disilazane are introduced in the preparation of the solvent-free polyurethane, and Si-N bonds are introduced into the molecular structure of the solvent-free polyurethane by utilizing the reaction of the castor oil, the tetramethyl disilazane and isocyanate. The Si-N bond can be connected with the base cloth through a valence bond, so that the solvent-free polyurethane adhesive layer and the base cloth layer are firmly combined together through the valence bond, and the polyurethane part in the instrument panel leather and the base cloth are firmly combined.
Drawings
FIG. 1 is a schematic cross-sectional view of a weakening-free PU instrument panel leather of example 1 of the present application.
FIG. 2 is a schematic cross-sectional view of the weakness-free PU instrument panel leather of example 2 of the present application.
FIG. 3 is a schematic cross-sectional view of the weakening-free PU instrument panel leather of comparative example 1 of the present application.
Reference numerals illustrate: 1. a polyurethane surface layer; 2. a solvent-free polyurethane adhesive layer; 3. a base cloth layer; 4. an aqueous decorative layer.
Detailed Description
The application is described in further detail below with reference to the drawings and examples.
Example 1
The embodiment discloses weakening-free PU instrument board leather. Referring to fig. 1, the weakening-free PU instrument panel leather includes a polyurethane face layer 1, a solvent-free polyurethane adhesive layer 2, and a base cloth layer 3 that are sequentially bonded together. In this embodiment, the thickness of the polyurethane face layer 1 is 0.15mm, and the thickness of the solvent-free polyurethane adhesive layer 2 is 0.25mm; the base cloth layer 3 is made of high-rise woven cloth and has a thickness of 0.95mm.
The raw materials for manufacturing the polyurethane surface layer 1 comprise polyurethane resin, N-dimethylformamide and ethyl acetate. In this embodiment, the polyurethane resin is specifically TPU 2180A type; the polyurethane resin, N-dimethylformamide and ethyl acetate comprise the following specific mass proportions: 95:60:10. in some embodiments, corresponding color paste can be added according to the requirement on the color of PU instrument board leather, and the mass ratio of the color paste to the polyurethane resin is preferable (95-105): any ratio of (19-25).
The solvent-free polyurethane adhesive layer 2 is made of solvent-free polyurethane, and is prepared by mixing and heating a group A raw material and a group B raw material. Wherein: the raw material of the group A is polyalcohol; the raw materials of the group B comprise isocyanate, a catalyst and a curing agent. In the embodiment, the polyol is toluene diisocyanate, the model is 80/20, the isocyanate is polyether polyol, the model is DL2000 330N, the catalyst is BiCAT 8106 bismuth catalyst, and the curing agent is dibenzylamine; the concrete mass ratio of the polyol, the isocyanate, the catalyst and the curing agent is as follows: 95:70:0.04:0.18.
The embodiment also discloses a preparation method of the weakening-free PU instrument board leather, which comprises the following steps:
s1, accurately weighing polyurethane resin, N-dimethylformamide and ethyl acetate according to a formula; after N, N-dimethylformamide and ethyl acetate are uniformly mixed, polyurethane resin is dissolved in the mixture to obtain the polyurethane coating material.
S2, taking release paper, pulling the release paper to move forwards by a traction roller, and controlling the pulling speed to be 11m/min; uniformly coating polyurethane coating material on release paper, and controlling the thickness of the coating layer on the release paper after drying to be 0.15mm; and then the release paper coated with the polyurethane coating material is sent into a baking oven for heating and drying, the temperature of the material is controlled to rise stepwise according to the process of 70-80-100-110-125 ℃, and the total drying time is controlled to be 4min, so that the polyurethane surface layer 1 is formed on the release paper.
S3, accurately weighing the raw materials of the group A and the raw materials of the group B according to a formula, uniformly coating the raw materials on the polyurethane surface layer 1 which is pulled by a traction roller to move forwards after mixing, controlling the thickness of a coating layer on the polyurethane surface layer 1 after drying to be 0.25mm, and controlling the traction speed to be 10 m/min; then the polyurethane surface layer 1 coated with the raw materials of the group A and the group B is sent into a baking oven for heating and drying, the materials are controlled to be heated stepwise according to the process of 100 ℃ to 110 ℃ to 125 ℃ and the total drying time is controlled to be 8min; the polyol and isocyanate react at this time under the action of the catalyst to form a solvent-free polyurethane adhesive layer 2 on one side surface of the polyurethane face layer 1.
S4, keeping the movement speed of the solvent-free polyurethane adhesive layer 2, and attaching the base cloth on the solvent-free polyurethane adhesive layer; the solvent-free polyurethane adhesive layer 2 attached with the base cloth is sent into a baking oven to be heated and dried, controlling the material to be at 135-140℃ process step heating at 145-145 deg.c, and controlling the total drying time to be 12min; and then separating the release paper to form the weakening-free PU instrument board leather.
The embodiment also discloses an instrument board, and the surface of the instrument board is coated with the weakening-free PU instrument board leather. In this instrument board, exempt from to weaken polyurethane part and the laminating of base cloth part firm in the PU instrument board leather, and exempt from to weaken PU instrument board leather smell little, more environmental protection.
Example 2
This embodiment is substantially the same as embodiment 1 except that: an aqueous decorative layer 4 is also attached to the polyurethane surface layer 1 on the side away from the solvent-free polyurethane adhesive layer 2.
Specifically, referring to fig. 2, the weakening-free PU instrument panel leather includes an aqueous decorative layer 4, a polyurethane surface layer 1, a solvent-free polyurethane adhesive layer 2, and a base fabric layer 3 that are sequentially bonded together. In this embodiment, the polyurethane topcoat has a thickness of 0.15mm, the solvent-free polyurethane adhesive layer 2 has a thickness of 0.25mm, the base cloth layer 3 has a thickness of 0.95mm, and the aqueous decorative layer 4 has a thickness of 0.1mm.
The raw materials of the water-based decorative layer 4 comprise water-based polyacrylate emulsion, a delustering agent, an organosilicon defoamer, an organosilicon leveling agent, an isocyanate crosslinking agent and industrial distilled water. In the embodiment, the water-based polyacrylate emulsion is specifically DB3422 type, the delustrant is specifically Tosoh K500 type, the organosilicon defoamer is specifically DF4266 type, the organosilicon leveling agent is specifically LA-01-120 type, and the isocyanate crosslinking agent is specifically purchased from Anhui Zhongen chemical Co., ltd; the specific mass ratio of the water-based polyacrylate emulsion, the delustering agent, the organic silicon defoamer, the organic silicon leveling agent, the isocyanate crosslinking agent and the industrial distilled water is as follows: 95:0.6:0.2:0.8:5:25.
The embodiment also discloses a preparation method of the weakening-free PU instrument board leather, which comprises the following steps:
S1-S4 are the same as in example 1.
S5, accurately weighing the aqueous polyacrylate emulsion, the flatting agent, the organosilicon defoamer, the organosilicon leveling agent, the isocyanate crosslinking agent and the industrial distilled water according to the formula, and uniformly mixing to obtain the finishing agent.
S6, coating the finishing agent on the surface of one side, far away from the solvent-free polyurethane adhesive layer 2, of the polyurethane surface layer 1 through a roller coater, controlling the thickness of the upper coating layer of the dried polyurethane surface layer 1 to be 0.1mm, and controlling the speed of the vehicle to be 10m/min; then the polyurethane surface layer 1 coated with the finishing agent is sent into a baking oven for heating and drying, the temperature of the materials is controlled to rise stepwise according to the process of 125-130 ℃ and the total drying time is controlled to be 3min; at the moment, acrylic ester reacts under the action of a cross-linking agent to form an aqueous decorative layer 4 on one side surface of the polyurethane surface layer 1; and then curling to obtain the weakening-free PU instrument board leather.
Examples 3 to 4
Examples 3-4 are substantially identical to example 2, except that: the raw materials for preparing the solvent-free polyurethane have different proportions.
In particular, the method comprises the steps of,
In example 3: the concrete mass ratio of the polyol, the isocyanate, the catalyst and the curing agent is as follows: 100:60:0.05:0.25.
In example 4: the concrete mass ratio of the polyol, the isocyanate, the catalyst and the curing agent is as follows: 105:48:0.06:0.3.
Examples 5 to 6
Examples 5-6 are substantially identical to example 3, except that: an ammonium phosphate flame retardant is added into the raw material of the group A for preparing the solvent-free polyurethane.
In particular, the method comprises the steps of,
In example 5: the group A raw materials comprise polyalcohol and ammonium phosphate flame retardant (specifically, diammonium hydrogen phosphate); the raw materials of the group B comprise isocyanate, a catalyst and a curing agent; the specific mass ratio of the polyol, isocyanate, catalyst, curing agent and ammonium phosphate flame retardant is as follows: 100:60:0.05:0.25:35.
In example 6: the group A raw materials comprise polyalcohol and ammonium phosphate flame retardant (specifically, diammonium hydrogen phosphate); the raw materials of the group B comprise isocyanate, a catalyst and a curing agent; the specific mass ratio of the polyol, isocyanate, catalyst, curing agent and ammonium phosphate flame retardant is as follows: 100:60:0.05:0.25:50.
Examples 7 to 8
Examples 7-8 are substantially identical to example 5 except that: the organosilicon leveling agent is added in the group A raw material for preparing the solvent-free polyurethane.
In particular, the method comprises the steps of,
In example 7: the group A raw materials comprise polyalcohol, ammonium phosphate flame retardant and organosilicon leveling agent (specifically BYK-2960 type); the raw materials of the group B comprise isocyanate, a catalyst and a curing agent; the concrete mass ratio of the polyol, the isocyanate, the catalyst, the curing agent, the ammonium phosphate flame retardant and the organosilicon leveling agent is as follows: 100:60:0.05:0.25:35:0.15.
In example 8: the group A raw materials comprise polyalcohol, ammonium phosphate flame retardant and organosilicon leveling agent (specifically BYK-2960 type); the raw materials of the group B comprise isocyanate, a catalyst and a curing agent; the concrete mass ratio of the polyol, the isocyanate, the catalyst, the curing agent, the ammonium phosphate flame retardant and the organosilicon leveling agent is as follows: 100:60:0.05:0.25:35:0.25.
Examples 9 to 13
Examples 9-13 are substantially identical to example 7, except that: castor oil and tetramethyl disilazane are added to the raw materials of group B for preparing the solvent-free polyurethane.
The hydroxyl group of the castor oil reacts with isocyanate to participate in the formation of carbamate, and simultaneously, the unsaturated double bond energy of the castor oil and the tetramethyl disilazane perform hydrosilylation reaction, so that the tetramethyl disilazane is stably connected in the molecular structure of the solvent-free polyurethane through the castor oil serving as a bridge, and Si-N bonds are introduced into the molecular structure of the solvent-free polyurethane. The Si-N bond has polarity, can react with the base cloth to form a covalent bond, and can firmly bond the solvent-free polyurethane adhesive layer 2 and the base cloth layer 3 together through the connection of the covalent bond.
In particular, the method comprises the steps of,
In example 9: the group A raw materials comprise polyalcohol, ammonium phosphate flame retardant and organosilicon leveling agent; the raw materials of the group B comprise isocyanate, catalyst, curing agent, castor oil (with the hydroxyl value of 176-187 mgKOH/g) and tetramethyl disilazane; the specific mass ratio of the polyol, the isocyanate, the catalyst, the curing agent, the ammonium phosphate flame retardant, the organosilicon leveling agent, the castor oil and the tetramethyl disilazane is as follows: 100:60:0.05:0.25:35:0.15:5:6.
In example 10: the group A raw materials comprise polyalcohol, ammonium phosphate flame retardant and organosilicon leveling agent; the raw materials of the group B comprise isocyanate, catalyst, curing agent, castor oil (with the hydroxyl value of 176-187 mgKOH/g) and tetramethyl disilazane; the specific mass ratio of the polyol, the isocyanate, the catalyst, the curing agent, the ammonium phosphate flame retardant, the organosilicon leveling agent, the castor oil and the tetramethyl disilazane is as follows: 100:60:0.05:0.25:35:0.15:7.5:9.
In example 11: the group A raw materials comprise polyalcohol, ammonium phosphate flame retardant and organosilicon leveling agent; the raw materials of the group B comprise isocyanate, catalyst, curing agent, castor oil (with the hydroxyl value of 176-187 mgKOH/g) and tetramethyl disilazane; the specific mass ratio of the polyol, the isocyanate, the catalyst, the curing agent, the ammonium phosphate flame retardant, the organosilicon leveling agent, the castor oil and the tetramethyl disilazane is as follows: 100:60:0.05:0.25:35:0.15:10:12.
In example 12: the group A raw materials comprise polyalcohol, ammonium phosphate flame retardant and organosilicon leveling agent; the raw materials of the group B comprise isocyanate, catalyst, curing agent, castor oil (with the hydroxyl value of 176-187 mgKOH/g) and tetramethyl disilazane; the specific mass ratio of the polyol, the isocyanate, the catalyst, the curing agent, the ammonium phosphate flame retardant, the organosilicon leveling agent, the castor oil and the tetramethyl disilazane is as follows: 100:60:0.05:0.25:35:0.15:7.5:7.5.
In example 13: the group A raw materials comprise polyalcohol, ammonium phosphate flame retardant and organosilicon leveling agent; the raw materials of the group B comprise isocyanate, catalyst, curing agent, castor oil (with the hydroxyl value of 176-187 mgKOH/g) and tetramethyl disilazane; the specific mass ratio of the polyol, the isocyanate, the catalyst, the curing agent, the ammonium phosphate flame retardant, the organosilicon leveling agent, the castor oil and the tetramethyl disilazane is as follows: 100:60:0.05:0.25:35:0.15:7.5:12.
Example 14
This embodiment is substantially the same as embodiment 10 except that: the proportions of the raw materials for preparing the polyurethane surface layer 1 are different.
In particular, the method comprises the steps of,
The raw materials for preparing the polyurethane surface layer 1 comprise polyurethane resin, N-dimethylformamide and ethyl acetate; the specific mass ratio of the three components is as follows: 105:65:15.
Example 15
This embodiment is substantially the same as embodiment 10 except that: the raw materials for preparing the water-based decorative layer 4 are different in proportion.
In particular, the method comprises the steps of,
The raw materials for preparing the water-based decorative layer 4 comprise water-based polyacrylate emulsion, a delustering agent, an organosilicon defoamer, an organosilicon leveling agent, an isocyanate crosslinking agent and industrial distilled water; the specific mass ratio of the six is as follows: 105:0.4:0.3:1:7:40.
Example 16
This embodiment is substantially the same as embodiment 10 except that: the control parameters of the preparation method of the weakening-free PU instrument board leather are different.
In particular to a special-shaped ceramic tile,
The preparation method of the weakening-free PU instrument board leather comprises the following steps of:
s1, accurately weighing polyurethane resin, N-dimethylformamide and ethyl acetate according to a formula; after N, N-dimethylformamide and ethyl acetate are uniformly mixed, polyurethane resin is dissolved in the mixture to obtain the polyurethane coating material.
S2, taking release paper, pulling the release paper to move forwards by a traction roller, and controlling the pulling speed to be 12m/min; uniformly coating polyurethane coating material on release paper, and controlling the thickness of the coating layer on the release paper after drying to be 0.12mm; and then the release paper coated with the polyurethane coating material is sent into a baking oven for heating and drying, the temperature of the material is controlled to rise stepwise according to the process of 60-70-90-100-115 ℃, and the total drying time is controlled to be 5min, so that the polyurethane surface layer 1 is formed on the release paper.
S3, accurately weighing the raw materials of the group A and the raw materials of the group B according to a formula, uniformly coating the raw materials on the polyurethane surface layer 1 which is pulled by a traction roller to move forwards after mixing, controlling the thickness of a coating layer on the polyurethane surface layer 1 after drying to be 0.22mm, and controlling the traction speed to be 11 m/min; then the polyurethane surface layer 1 coated with the raw materials of the group A and the group B is sent into a baking oven for heating and drying, the materials are controlled to be heated stepwise according to the process of 90 ℃ to 100 ℃ to 115 ℃ and the total drying time is controlled to be 10min; the polyol and isocyanate react at this time under the action of the catalyst to form a solvent-free polyurethane adhesive layer 2 on one side surface of the polyurethane face layer 1.
S4, keeping the movement speed of the solvent-free polyurethane adhesive layer 2, and attaching the base cloth on the solvent-free polyurethane adhesive layer; the solvent-free polyurethane adhesive layer 2 attached with the base cloth is sent into a baking oven to be heated and dried, controlling the material to be at the temperature of 125-130℃ -135 deg.C process step-by-step heating, and controlling the total drying time to be 14min; and then separating the release paper.
S5, accurately weighing the aqueous polyacrylate emulsion, the flatting agent, the organosilicon defoamer, the organosilicon leveling agent, the isocyanate crosslinking agent and the industrial distilled water according to the formula, and uniformly mixing to obtain the finishing agent.
S6, coating the finishing agent on the surface of one side, far away from the solvent-free polyurethane adhesive layer 2, of the polyurethane surface layer 1 through a roller coater, controlling the thickness of the upper coating layer of the polyurethane surface layer 1 after drying to be 0.08mm, and controlling the speed of the vehicle to be 12m/min; then the polyurethane surface layer 1 coated with the finishing agent is sent into a baking oven for heating and drying, the temperature of the materials is controlled to rise stepwise according to the process of 115 ℃ to 120 ℃ and the total drying time is controlled to be 4min; at the moment, acrylic ester reacts under the action of a cross-linking agent to form an aqueous decorative layer 4 on one side surface of the polyurethane surface layer 1; and then curling to obtain the weakening-free PU instrument board leather.
Example 17
This embodiment is substantially the same as embodiment 10 except that: the control parameters of the preparation method of the weakening-free PU instrument board leather are different.
In particular to a special-shaped ceramic tile,
The preparation method of the weakening-free PU instrument board leather comprises the following steps of:
s1, accurately weighing polyurethane resin, N-dimethylformamide and ethyl acetate according to a formula; after N, N-dimethylformamide and ethyl acetate are uniformly mixed, polyurethane resin is dissolved in the mixture to obtain the polyurethane coating material.
S2, taking release paper, pulling the release paper to move forwards by a traction roller, and controlling the pulling speed to be 10m/min; uniformly coating polyurethane coating material on release paper, and controlling the thickness of the upper coating layer of the release paper after drying to be 0.18mm; and then the release paper coated with the polyurethane coating material is sent into a baking oven for heating and drying, the temperature of the material is controlled to rise stepwise according to the process of 80-90-110-120-135 ℃, and the total drying time is controlled to be 3min, so that the polyurethane surface layer 1 is formed on the release paper.
S3, accurately weighing the raw materials of the group A and the raw materials of the group B according to a formula, uniformly mixing the raw materials, coating the raw materials on the polyurethane surface layer 1 which is pulled by a traction roller to move forwards, and controlling the thickness of the coating layer on the polyurethane surface layer 1 after drying to be 0.28mm and the traction speed to be 9 m/min; then the polyurethane surface layer 1 coated with the raw materials of the group A and the group B is sent into a baking oven for heating and drying, the materials are controlled to be heated stepwise according to the process of 110 ℃ to 120 ℃ to 135 ℃ and the total drying time is controlled to be 6min; at this time, the polyol and isocyanate react under the action of the catalyst, and a solvent-free polyurethane adhesive layer 2 is formed on one side surface of the polyurethane surface layer 1.
S4, keeping the movement speed of the solvent-free polyurethane adhesive layer 2, and attaching the base cloth on the solvent-free polyurethane adhesive layer; the solvent-free polyurethane adhesive layer 2 attached with the base cloth is sent into a baking oven to be heated and dried, controlling the material to be 145-150℃ step-wise heating at the temperature of-155 ℃ in the process of-155 ℃, and controlling the total drying time to be 10min; and then separating the release paper.
S5, accurately weighing the aqueous polyacrylate emulsion, the flatting agent, the organosilicon defoamer, the organosilicon leveling agent, the isocyanate crosslinking agent and the industrial distilled water according to the formula, and uniformly mixing to obtain the finishing agent.
S6, coating the finishing agent on the surface of one side, far away from the solvent-free polyurethane adhesive layer 2, of the polyurethane surface layer 1 through a roller coater, controlling the thickness of the upper coating layer of the polyurethane surface layer 1 after drying to be 0.12mm, and controlling the speed of the vehicle to be 8m/min; then the polyurethane surface layer 1 coated with the finishing agent is sent into a baking oven for heating and drying, the temperature of the materials is controlled to rise stepwise according to the process of 135 ℃ to 140 ℃, and the total drying time is controlled to be 2min; at the moment, acrylic ester reacts under the action of a cross-linking agent to form an aqueous decorative layer 4 on one side surface of the polyurethane surface layer 1; and then curling to obtain the weakening-free PU instrument board leather.
Comparative example 1
The main difference between this comparative example and example 1 is that: the weakening-free PU instrument panel leather does not contain the solvent-free polyurethane adhesive layer 2.
Specifically, referring to fig. 3, the weakening-free PU instrument panel leather includes a polyurethane facing layer 1 and a base fabric layer 3 that are bonded together. Specifically, the thickness of the polyurethane surface layer 1 is 0.15mm, and the raw materials for preparing the polyurethane surface layer 1 comprise polyurethane resin, N-dimethylformamide and ethyl acetate, wherein the mass ratio of the polyurethane resin to the N, N-dimethylformamide to the ethyl acetate is as follows: 95:60:10; the base cloth layer 3 is made of high-rise woven cloth and has a thickness of 0.95mm.
Performance detection
The weakening-free PU instrument board leather obtained in examples 1 to 17 and comparative example 1 was taken for peeling detection; the results of the measurements are shown in Table 1.
And (3) peeling detection:
(1) Sample preparation: rectangular weakening-free PU instrument board leather samples with the length of 200mm and the width of 50mm are prepared.
(2) The test method comprises the following steps:
1) The solvent-free polyurethane adhesive layer 2 (comparative example 1 was polyurethane top layer 1) and the base fabric layer 3 were peeled in advance by 50mm along the test length direction, and the peeled portion was not significantly damaged.
2) And clamping the two ends of the sample stripping part on a testing machine respectively, so that the longitudinal axis of the sample stripping part coincides with the central connecting line of the upper clamp and the lower clamp. The test was carried out at a speed of 200 mm/min; in the test, the non-peeled portion was T-shaped with respect to the stretching direction, and the peeling force during peeling of the sample was recorded.
TABLE 1 peeling Properties of the weakening-free PU Instrument panel leather obtained in examples 1 to 17 and comparative example 1
| Project | Transverse peel force/N | Longitudinal peel force/N |
| Example 1 | 54.6 | 52.8 |
| Example 2 | 54.9 | 53.3 |
| Example 3 | 55.8 | 54.1 |
| Example 4 | 55.1 | 53.6 |
| Example 5 | 56.1 | 54.3 |
| Example 6 | 55.7 | 54.2 |
| Example 7 | 56.6 | 54.8 |
| Example 8 | 56.8 | 54.7 |
| Example 9 | 59.1 | 58.2 |
| Example 10 | Can not be peeled off | Can not be peeled off |
| Example 11 | Can not be peeled off | Can not be peeled off |
| Example 12 | 58.9 | 57.8 |
| Example 13 | 59.6 | 58.7 |
| Example 14 | Can not be peeled off | Can not be peeled off |
| Example 15 | Can not be peeled off | Can not be peeled off |
| Example 16 | Can not be peeled off | Can not be peeled off |
| Example 17 | Can not be peeled off | Can not be peeled off |
| Comparative example 1 | 30.7 | 30.1 |
Referring to Table 1, from the results of the tests of examples 1 to 17, it can be seen that: the polyurethane part and the base cloth part (base cloth layer 3) of the weakening-free PU instrument board leather obtained by the embodiments of the application have higher stripping force, and part of the embodiments are even not stripped, which indicates that the polyurethane part and the base cloth part of the weakening-free PU instrument board leather obtained by the application have good bonding property.
Analysis of the detection results of example 1 and comparative example 1 revealed that: after the solvent-free polyurethane adhesive layer 2 is introduced, the peeling force between the polyurethane part and the base cloth part of the obtained weakening-free PU instrument board leather is greatly improved, namely the bonding fastness between the polyurethane part and the base cloth part is greatly improved. The solvent-free polyurethane is a water-free solvent-free system, and bubbles are not generated when the solvent-free polyurethane is attached to the base cloth, so that compared with a polyurethane surface layer, the solvent-free polyurethane is more tightly attached to the base cloth, so that better combination property is achieved with the base cloth, and the polyurethane surface layer 1 and the base cloth layer 3 are enabled to have better combination fastness through connection of the solvent-free polyurethane adhesive layer 2.
Analysis of the results of examples 7,9-11 revealed that: castor oil and tetramethyl disilazane are introduced in the synthesis of the solvent-free polyurethane, so that the stripping force between the polyurethane part and the base cloth part can be obviously improved. This is due to: the castor oil can react with isocyanate and tetramethyl disilazane respectively, so that the tetramethyl disilazane with Si-N bond is stably connected in the molecular structure of the solvent-free polyurethane through the bridge action of the castor oil; the Si-N bond has stronger polarity and can be connected with the base cloth by covalent bonds; through covalent bond connection, the bonding property of the solvent-free polyurethane adhesive layer 2 and the base cloth layer 3 is improved, and the bonding property between the polyurethane part and the base cloth part is further improved.
Analysis of the results of examples 10, 12-13 revealed that: the proper proportion of the castor oil and the tetramethyl disilazane is favorable for better playing the bridge function of the castor oil, thereby further improving the bonding property between the polyurethane part and the base cloth part of the PU instrument board leather without weakening.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (5)
1. Exempt from to weaken PU instrument board leather, its characterized in that: comprises a polyurethane surface layer (1), a solvent-free polyurethane adhesive layer (2) and a base cloth layer (3);
the solvent-free polyurethane forming the solvent-free polyurethane adhesive layer (2) is prepared from the following raw materials in parts by weight: 95-105 parts of polyalcohol, 48-70 parts of isocyanate, 0.04-0.06 part of catalyst and 0.18-0.3 part of curing agent;
The solvent-free polyurethane is prepared by mixing and heating a raw material A and a raw material B;
the group A raw materials comprise polyalcohol, and the group B raw materials comprise isocyanate, a catalyst and a curing agent;
the raw materials of the group B also comprise 5-10 parts by mass of castor oil and 6-12 parts by mass of tetramethyl disilazane;
the isocyanate is toluene diisocyanate; the polyol is a polyether polyol;
The catalyst is a metal bismuth catalyst, and the curing agent is dibenzylamine.
2. The weakness-free PU instrument panel leather of claim 1, wherein: the group A raw materials also comprise 35-50 parts by mass of ammonium phosphate flame retardant.
3. The weakness-free PU instrument panel leather of claim 1, wherein: the group A raw material also comprises 0.15-0.25 parts by mass of organosilicon leveling agent.
4. The weakness-free PU instrument panel leather of claim 1, wherein: the novel decorative board also comprises a water-based decorative layer (4), wherein the water-based decorative layer (4) is made of water-based polyacrylate.
5. The method for preparing the weakening-free PU instrument board leather according to any one of claims 1 to 4, which is characterized in that: comprising the following steps:
dissolving polyurethane resin in a solvent, coating the solvent on release paper, and heating and drying to obtain a polyurethane surface layer (1);
the raw materials are taken according to the formula, mixed and coated on the polyurethane surface layer (1), and heated to 90-135 ℃ to form a solvent-free polyurethane adhesive layer (2);
And (3) attaching a base cloth to the solvent-free polyurethane adhesive layer (2) to form a base cloth layer (3).
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