CN113897121B - Yellowing-resistant self-repairing coating composition, automobile paint protective film and preparation method thereof - Google Patents
Yellowing-resistant self-repairing coating composition, automobile paint protective film and preparation method thereof Download PDFInfo
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- CN113897121B CN113897121B CN202111211217.3A CN202111211217A CN113897121B CN 113897121 B CN113897121 B CN 113897121B CN 202111211217 A CN202111211217 A CN 202111211217A CN 113897121 B CN113897121 B CN 113897121B
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- hydroxyl
- yellowing
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- self
- resistant self
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- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The application relates to a yellowing-resistant self-repairing coating composition which is characterized by comprising the following raw materials in parts by weight: 10-30 parts by weight of a hydroxyl-terminated polyurethane prepolymer; 70-90 parts by weight of branched hydroxyl polyester; 11.7-40.8 parts by weight of a curing agent; 0-1 part by weight of a chain extender; 0.1 to 0.3 part by weight of a first catalyst; 10-40 parts by weight of a first solvent; wherein the hydroxyl-terminated polyurethane prepolymer and the branched hydroxyl polyester account for 100 parts by weight. The application also relates to an automobile paint protective film and a preparation method thereof. The automobile paint protective film prepared by the composition has excellent physical scratch resistance, yellowing resistance, oil resistance and antifouling performance, and all auxiliaries do not have precipitation risk.
Description
Technical Field
The application relates to the field of coatings and automobile paint protective films, in particular to a yellowing-resistant self-repairing coating composition for an automobile paint protective film, an automobile paint protective film and a preparation method of the automobile paint protective film.
Background
With the development of economy and the enhancement of purchasing power of people, automobiles have gone into thousands of households. As a high value item, maintenance and repair of automobiles is particularly important. The automobile finish protective film is also called as invisible automobile coat or automobile coat film, can effectively reduce or avoid the damage of physical scraping, illumination, oxygen and corrosive substances to the automobile original factory paint when being stuck on the automobile finish, and is easy to repair and low in replacement cost.
At present, manufacturers of the car clothes film mainly comprise 3M, Longmian, Weigu, XPEL and the like abroad, and Kangkui, Lekai, Boka and the like are mainly produced at home. Because the domestic starting is late, the product quality is poorer than that of the products at abroad, but according to the market feedback, even a high-end TPU car clothing film still has the problems of great difference in antifouling property, scratch resistance, yellowing resistance and repairability. To solve the above problems, a current general solution is to optimize a self-healing coating coated on a TPU-based film. For example, chinese patent CN 202011571702.7 discloses a yellowing-resistant invisible car cover protective film with a self-repairing function, wherein a small-molecule ultraviolet absorber is added in the self-repairing coating, so as to effectively improve the yellowing resistance of the car cover film. However, the ultraviolet absorber added in this technique is a small molecule, does not participate in the reaction of the resin system, and still has a risk of precipitation during use.
Disclosure of Invention
The object of the present application is to provide a yellowing resistant self-healing coating composition, thereby solving the above technical problems.
The invention also aims to provide an automobile paint protective film prepared from the yellowing-resistant self-repairing coating composition.
The application also aims to provide a preparation method of the automobile paint protective film.
In order to solve the above technical problem, the present application provides the following technical solutions:
in a first aspect, the present application provides a yellowing-resistant self-healing coating composition, comprising the following raw materials in parts by weight:
wherein the hydroxyl-terminated polyurethane prepolymer and the branched hydroxyl polyester account for 100 parts by weight.
In one embodiment of the first aspect, the hydroxyl terminated polyurethane prepolymer is synthesized from the following raw materials: a polyether triol; a polyester diol; a reactive wetting and leveling agent; a reactive slip agent; a reactive ultraviolet absorber; an antioxidant; an aliphatic diisocyanate; a second solvent and a second catalyst.
In one embodiment of the first aspect, the polyether triol is selected from, but not limited to, one or more of polyoxypropylene/oxyethylene copolytriol, polyoxypropylene triol, and the polyether triol has a number average molecular weight of 1000-.
In one embodiment of the first aspect, the polyester diol is selected from one or more of polycaprolactone diol, poly neopentyl glycol adipate diol, poly hexanediol adipate diol, poly diethylene glycol adipate diol, poly butanediol neopentyl glycol adipate diol, poly methyl propylene glycol adipate diol, and polycarbonate diol, and the number average molecular weight of the polyester polyol is 1000-4000.
In one embodiment of the first aspect, the reactive wetting and leveling agent is an organosilicon modified polyether polyol.
In one embodiment of the first aspect, the reactive antifouling slip agent is selected from one of perfluoropolyether alcohols and perfluoropolyether amidoethyl alcohols.
In one embodiment of the first aspect, the reactive uv absorber is selected from one or both of benzophenone and benzotriazole uv absorbers having a reactive hydroxyl group.
In one embodiment of the first aspect, the aliphatic diisocyanate is selected from one or two of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
In one embodiment of the first aspect, the antioxidant is selected from one of antioxidant 1010, antioxidant 1076, antioxidant 245, and antioxidant 1135.
In one embodiment of the first aspect, the second catalyst is selected from one of organotin and organobismuth catalysts.
In one embodiment of the first aspect, the second solvent is selected from one or more of, but not limited to, ethyl acetate, butyl acetate, dimethyl carbonate, methyl ethyl ketone, toluene, and xylene.
In one embodiment of the first aspect, the polyether triol has a number average molecular weight of 3000-.
In one embodiment of the first aspect, the silicone-modified polyether polyol is selected from one of a hydroxyl terminated monofunctional silicone-modified polyether, a hydroxyl terminated difunctional silicone-modified polyether, and a pendant hydroxyl difunctional silicone-modified polyether.
In one embodiment of the first aspect, the hydroxyl terminated polyurethane prepolymer is prepared by the following method:
1) uniformly mixing polyether triol, polyester diol, a reactive wetting and leveling agent, a reactive slip agent, a reactive ultraviolet absorber, aliphatic isocyanate and an antioxidant in a second solvent at a reaction temperature of 50-60 ℃ to obtain a first reaction mixture;
2) and adding a second catalyst into the first reaction mixture, gradually heating to 85-95 ℃, reacting at normal pressure, and discharging when the NCO content is reduced to zero to obtain the hydroxyl-terminated polyurethane prepolymer.
In one embodiment of the first aspect, in step 2), after a gradual temperature rise to 85-95 ℃ and an atmospheric reaction time of 4-6 hours, the NCO content is determined every half hour until the NCO content has fallen to zero.
In one embodiment of the first aspect, the branched hydroxy polyester is selected from one or both of kosmophen 670 and basf Sovermol 1052.
In one embodiment of the first aspect, the chain extender is selected from one of 1, 4-butanediol, diethylene glycol, and neopentyl glycol;
in one embodiment of the first aspect, the curing agent is selected from one of basonoat HI100, basonoat HI 190B/S, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
In one embodiment of the first aspect, the first catalyst is selected from one of organotin and organobismuth catalysts.
In one embodiment of the first aspect, the first solvent is selected from one or more of, but not limited to, ethyl acetate, butyl acetate, dimethyl carbonate, methyl ethyl ketone, toluene, and xylene.
In a second aspect, the application provides an automobile paint protective film, the automobile paint protective film sequentially comprises a PET release film, a yellowing-resistant self-repairing coating, a TPU base film, an acrylic acid pressure-sensitive adhesive and a PET release film from top to bottom, and the yellowing-resistant self-repairing coating is prepared from the yellowing-resistant self-repairing coating composition of the first aspect.
In a third aspect, the present application provides a method for preparing an automotive finish protective film, characterized in that the method comprises the steps of:
s1: dispersing the raw material components of the yellowing-resistant self-repairing coating composition in the first aspect by a dispersion machine at a high speed of 1000rpm at 400-;
s2: coating acrylic acid pressure-sensitive glue on a PET release film, drying at 100 ℃ to form an acrylic acid glue layer, and compounding the acrylic acid glue layer with a TPU base film; and then coating the self-repairing coating liquid on the other side of the TPU base film, drying and curing at 90 ℃/120 ℃/150 ℃ in a stepped temperature rise mode to obtain a yellowing-resistant self-repairing coating, compounding another PET release film on the surface of the yellowing-resistant self-repairing coating, putting the PET release film into an oven, and curing at 50 ℃ to obtain the automobile paint surface protective film.
In one embodiment of the third aspect, the applying the self-repairing coating liquid on the TPU-based film in step S2 includes applying the self-repairing coating liquid on the TPU-based film with a wire bar.
Compared with the prior art, the beneficial effect of this application lies in:
(1) the composition material adopts branched polyester polyol to match with a polyfunctional isocyanate curing agent, and the coating cured by heating has rapid self-repairing capability on scratches under the heating condition of hot water, and meanwhile, the self-repairing coating is smooth and compact and has excellent physical scratch resistance;
(2) the whole composite system is pure aliphatic, does not contain unsaturated bonds such as double bonds, benzene rings and the like, and in addition, a reactive ultraviolet absorbent is introduced through a hydroxyl-terminated polyurethane prepolymer, so that a coating after construction and curing has excellent yellowing resistance;
(3) the fluorocarbon chain segment is introduced through the reactive antifouling slip agent, and the self-assembly effect induces the fluorocarbon chain segment to migrate to the surface of the coating, so that the surface tension of the coating is greatly reduced, and the coating has excellent waterproof, oilproof and antifouling properties;
and (4) the leveling, smooth and anti-yellowing auxiliary agents are reactive auxiliary agents, so that the precipitation risk is avoided.
Drawings
FIG. 1 shows an infrared absorption spectrum of a hydroxyl terminated polyurethane prepolymer according to example 1.
FIG. 2 shows an infrared absorption spectrum of a hydroxyl terminated polyurethane prepolymer according to example 2.
FIG. 3 shows an infrared absorption spectrum of a hydroxyl terminated polyurethane prepolymer according to example 3.
Fig. 4 shows a schematic view of an automotive paint protective film according to one embodiment of the present application.
Detailed Description
As described above, the protective film for automobile paint surface is required to have excellent physical scratch resistance, yellowing resistance, and antifouling and oil-proof properties, and more importantly, various additives added to the protective film for automobile paint surface cannot be separated out during long-term use.
To this end, in a first aspect, the present application firstly aims to provide a yellowing-resistant self-repairing coating composition for an automotive finish protective film, which is composed of the following raw materials in parts by weight:
wherein the total weight of the hydroxyl-terminated polyurethane prepolymer and the branched hydroxyl polyester is 100 parts.
In one embodiment, the hydroxyl terminated polyurethane prepolymer may be used in an amount of 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, or a range or subrange therebetween. Accordingly, the branched hydroxyl polyester can be used in an amount of 90 parts by weight, 85 parts by weight, 80 parts by weight, 75 parts by weight, 70 parts by weight, or a range or subrange between any two of them.
In one embodiment, when the total amount of hydroxyl terminated polyurethane prepolymer and branched hydroxyl polyester is 100 parts by weight, the amount of curing agent used may be 11.7 parts by weight, 15 parts by weight, 21.7 parts by weight, 25 parts by weight, 31.7 parts by weight, 35 parts by weight, 40.8 parts by weight, or a range or subrange between any two of them.
In one embodiment, when the total amount of hydroxyl terminated polyurethane prepolymer and branched hydroxyl polyester is 100 parts by weight, the chain extender may be used in an amount of 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, or a range or subrange therebetween.
In one embodiment, the first catalyst may be used in an amount of 0.1 parts by weight, 0.2 parts by weight, or 0.3 parts by weight, based on 100 parts by weight of the total amount of the hydroxyl terminated polyurethane prepolymer and the branched hydroxyl polyester.
In one embodiment, when the total amount of the hydroxyl terminated polyurethane prepolymer and the branched hydroxyl polyester is 100 parts by weight, the first solvent may be used in an amount of 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or a range or sub-range between any two of them.
The hydroxyl-terminated polyurethane prepolymer is one of important components of the yellowing-resistant self-repairing coating composition, and can be cured with branched hydroxyl polyester simultaneously under the action of a polyfunctional isocyanate curing agent, so that the self-repairing function of the obtained coating is further improved.
In one embodiment, the hydroxyl terminated polyurethane prepolymer is synthesized from the following raw materials: polyether triol, polyester diol, a reactive wetting and leveling agent, a reactive slip agent, a reactive ultraviolet absorber, an antioxidant, aliphatic diisocyanate, a second solvent and a second catalyst. In one embodiment, the polyether triol is selected from one or more of polypropylene oxide/ethylene oxide copolymer triol and polypropylene oxide triol, and the polyether triol has a number average molecular weight of 1000-. For example, the polyether triol may have a number average molecular weight of 3000, 3500, 4000, 4500, 5000, 5500, 6000 or a range or subrange between any two of them.
In one embodiment, the polyester diol is selected from one or more of, but not limited to, polycaprolactone diol, poly (neopentyl glycol adipate) diol, poly (hexamethylene adipate) diol, poly (diethylene glycol adipate) diol, poly (butylene glycol neopentyl glycol adipate) diol, poly (methyl propylene adipate) diol, and polycarbonate diol. The number average molecular weight of the polyester dihydric alcohol is 1000-4000. For example, the polyester diol may have a number average molecular weight of 1000, 1500, 2000, 2500, 3000, 3500, 4000, or a range or subrange between any two of them.
In one embodiment, the reactive wetting and leveling agent is an organosilicon modified polyether polyol, and is selected from one of hydroxyl-terminated mono-functional organosilicon modified polyether, hydroxyl-terminated di-functional organosilicon modified polyether, and side hydroxyl-terminated di-functional organosilicon modified polyether. In one embodiment, the hydroxyl terminated monofunctional silicone modified polyether and the hydroxyl terminated difunctional silicone modified polyether are available from siloco high molecular polymers, inc, guangzhou; the pendant hydroxyl difunctional silicone modified polyether is available from mezzanine corporation.
In one embodiment, the reactive anti-soil slip agent is selected from one of perfluoropolyether alcohols and perfluoropolyether amidoethyl alcohols. In one embodiment, the perfluoropolyether alcohols are purchased from Suzhou Bingmu new materials; the perfluoropolyether amidoethyl alcohol is purchased from neutralized environmental protection company Limited.
In one embodiment, the reactive uv absorber is selected from one or both of benzophenone and benzotriazole uv absorbers having a reactive hydroxyl group. In a preferred embodiment, the benzophenone-type ultraviolet absorber with active hydroxyl (UV950L) is obtained from Dedamagingcheng chemical engineering, and the benzotriazole-type ultraviolet absorber with active hydroxyl (R-455) is obtained from Chiita science and technology.
In one embodiment, the aliphatic diisocyanate is selected from one or two of 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (HMDI). In one embodiment, the antioxidant is selected from one of antioxidant 1010, antioxidant 1076, antioxidant 245, and antioxidant 1135.
In one embodiment, the first solvent and the second solvent are each independently selected from one or more of, but not limited to, ethyl acetate, butyl acetate, dimethyl carbonate, methyl ethyl ketone, toluene, and xylene.
In one embodiment, the preparation method of the hydroxyl-terminated polyurethane prepolymer comprises the following steps:
1) putting polyether triol, polyester diol, a reactive wetting and leveling agent, a reactive slip agent, a reactive ultraviolet absorber, aliphatic isocyanate, an antioxidant and a solvent into a reaction kettle, and uniformly stirring at 50-60 ℃;
2) adding a catalyst, gradually heating to 85-95 ℃, reacting for 4-6 hours under normal pressure, measuring the NCO content once every half hour, and discharging when the NCO is reduced to zero to obtain the hydroxyl-terminated polyurethane prepolymer.
In one embodiment, the branched hydroxyl polyester is selected from one or two of koste Desmophen670, basf Sovermol 1052;
in one embodiment, the chain extender is selected from one of 1,4 butanediol, diethylene glycol, neopentyl glycol;
in one embodiment, the curing agent is selected from one of basonoat HI100, basonoat HI 190B/S, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI);
in one embodiment, the first catalyst and the second catalyst are each independently selected from one of an organotin and an organobismuth catalyst.
In a second aspect, as shown in fig. 4, the present application provides an automotive finish protective film. The automobile paint surface protective film sequentially comprises a PET release film 50, a yellowing-resistant self-repairing coating 40, a TPU base film 30, an acrylic pressure-sensitive adhesive layer 20 and a PET release film 10 from top to bottom. The release films 10, 50 may be PET films commonly used in the art. The yellowing-resistant self-healing coating 40 may be made from the yellowing-resistant self-healing coating composition described in the first aspect. The TPU-based film 30 is a commercially available aliphatic thermoplastic polyurethane resin. The acrylic pressure sensitive adhesive 20 is a commercially available solvent-type acrylic pressure sensitive adhesive.
Examples
The present application will now be described and illustrated in further detail with reference to the following examples. All chemical raw materials can be purchased from the market unless otherwise specified. Those skilled in the art will appreciate that the following embodiments are exemplary only.
Preparation examples
Example 1
Preparation of hydroxyl-terminated polyurethane prepolymer
The raw materials and the amounts used in this example are shown in Table 1.
TABLE 1
The hydroxyl-terminated polyurethane prepolymer of this example was prepared as follows:
1) putting 600g of polyoxypropylene triol, 200g of poly neopentyl glycol adipate diol, 40g of leveling agent side hydroxyl two-functionality organic silicon modified polyether, 20g of antifouling and slip agent perfluoropolyether alcohol, 61.5g of ultraviolet absorbent UV950L40g, 61.5g of butyl acetate, 10100.5 g of antioxidant and 38g of 1, 6-hexamethylene diisocyanate into a reaction kettle, and uniformly stirring at 50 ℃;
2) adding 0.04g of organic bismuth catalyst, gradually heating to 95 ℃, reacting for 6 hours under normal pressure, measuring the NCO content once every half hour, and discharging when the NCO is reduced to zero to obtain the hydroxyl-terminated polyurethane prepolymer according to the embodiment 1. The infrared spectrum of the hydroxyl-terminated polyurethane prepolymer of example 1 is shown in FIG. 1, and it can be seen from FIG. 1 that the NCO functional group is 2240-2280cm -1 The infrared characteristic peak disappears completely, which indicates that NCO and hydroxyl react completely, and the generated carbamate bond is 1715cm -1 Strong characteristic peaks appear nearby.
Example 2
Preparation of hydroxyl-terminated polyurethane prepolymer
The raw materials and the amounts used in this example are shown in Table 2.
TABLE 2
The hydroxyl-terminated polyurethane prepolymer of this example was prepared as follows:
1) putting 600g of polyoxypropylene/ethylene oxide copolymer triol, 200g of poly (methyl propylene glycol adipate) glycol, 40g of leveling agent terminal hydroxyl bifunctional organic silicon modified polyether, 20g of antifouling slip agent perfluoropolyether amide ethyl alcohol, R-45540 g of ultraviolet absorbent, 65g of dimethyl carbonate, 10760.5 g of antioxidant and 34.5g of isophorone diisocyanate into a reaction kettle, and uniformly stirring at 50 ℃;
2) adding 0.04g of organic bismuth catalyst, gradually heating to 95 ℃, reacting for 6 hours under normal pressure, measuring the NCO content once every half hour, and discharging when the NCO is reduced to zero to obtain the hydroxyl-terminated polyurethane prepolymer according to the embodiment 2. The infrared spectrum of the hydroxyl-terminated polyurethane prepolymer of example 2 is shown in FIG. 2, and it can be seen from FIG. 2 that the NCO functional group is 2240-2280cm -1 The infrared characteristic peak disappears completely, which indicates that NCO and hydroxyl react completely, and the generated carbamate bond is 1715cm -1 Strong characteristic peaks appear nearby.
Example 3
Preparation of hydroxyl-terminated polyurethane prepolymer
The raw materials and the amounts used in this example are shown in Table 3.
TABLE 3
The hydroxyl-terminated polyurethane prepolymer of this example was prepared as follows:
1) putting 600g of polypropylene oxide/ethylene oxide copolymer triol, 200g of polycarbonate diol, 40g of flatting agent end hydroxyl group monofunctional organic silicon modified polyether, 20g of antifouling and slip agent perfluoropolyether alcohol, 40g of ultraviolet absorbent UV950L40, 66g of toluene, 2450.5 g of antioxidant and 33.5g of dicyclohexylmethane diisocyanate into a reaction kettle, and uniformly stirring at 50 ℃;
2) adding 0.04g of organic bismuth catalyst, gradually heating to 90 ℃, reacting for 4 hours under normal pressure, measuring the NCO content once every half hour, and discharging when the NCO is reduced to zero to obtain the hydroxyl-terminated polyurethane prepolymer according to the embodiment 3. The infrared spectrum of the hydroxyl-terminated polyurethane prepolymer of example 3 is shown in FIG. 3, and it can be seen from FIG. 3 that the NCO functional group is 2240-2280cm -1 The infrared characteristic peak disappears completely, which indicates that NCO and hydroxyl react completely, and the generated carbamate bond is 1715cm -1 Strong nearby characterAnd a characteristic peak appears.
Application examples
Example 4
(1) Preparation of self-repairing coating liquid:
and (3) putting the materials into the charging barrel according to the batching table, dispersing for 10min at a high speed of 400rpm by using a dispersion machine, and standing for later use.
(2) Preparation of protective film for automobile paint surface
Coating acrylic acid pressure-sensitive glue on a PET release film 10 by using a wire rod, drying at 100 ℃ to form an acrylic acid glue layer with the thickness of 30um, and compounding the acrylic acid glue layer with a TPU base film with the thickness of 150 um; then, the coating liquid prepared above is coated on the other side of the TPU base film by using a wire bar, and is dried and cured for 5min at 90 ℃/120 ℃/150 ℃ in a step heating manner to obtain a coating layer with the thickness of about 10um, and a PET release film 50 is compounded on the surface of the coating layer, and the coating layer is put into an oven and cured for 48 hours at 50 ℃, so that the automobile paint surface protective film according to the example 4 is obtained, and the performance of the protective film is tested, and the results are shown in table 4.
Example 5
(1) Preparation of self-repairing coating liquid:
and (3) putting the materials into the charging barrel according to the batching table, dispersing for 10min at a high speed of 400rpm by using a dispersion machine, and standing for later use.
(2) Preparation of protective film for automobile paint surface
Coating acrylic acid pressure-sensitive glue on a PET release film 10 by using a wire rod, drying at 100 ℃ to form an acrylic acid glue layer with the thickness of 30um, and compounding the acrylic acid glue layer with a TPU base film with the thickness of 150 um; then, the coating liquid prepared above is coated on the other side of the TPU base film by using a wire bar, and is dried and cured for 5min at 90 ℃/120 ℃/150 ℃ in a step heating manner to obtain a coating layer with the thickness of about 10um, and a PET release film 50 is compounded on the surface of the coating layer, and the coating layer is put into an oven and cured for 48 hours at 50 ℃, so that the automobile paint surface protective film according to the example 5 is obtained, and the performance of the protective film is tested, and the results are shown in table 4.
Example 6
(1) Preparation of self-repairing coating liquid:
and (3) putting the materials into the charging barrel according to the batching table, dispersing for 10min at a high speed of 400rpm by using a dispersion machine, and standing for later use.
(2) Preparation of protective film for automobile paint surface
Coating acrylic acid pressure-sensitive glue on a PET release film 10 by using a wire rod, drying at 100 ℃ to form an acrylic acid glue layer with the thickness of 30um, and compounding the acrylic acid glue layer with a TPU base film with the thickness of 150 um; then, the coating liquid prepared above is coated on the other side of the TPU-based film by a wire bar, dried and cured for 5min at 90 ℃/120 ℃/150 ℃ in a step-heating manner to obtain a coating layer with a thickness of about 10um, and the PET release film 50 is compounded on the surface of the coating layer, and then the coating layer is put into an oven and cured for 48 hours at 50 ℃, so that the automobile paint surface protective film according to example 6 is obtained, and the performance of the protective film is tested, and the results are shown in table 4.
Example 7
(1) Preparation of self-repairing coating liquid:
and (3) putting the materials into the charging barrel according to the batching table, dispersing for 10min at a high speed of 400rpm by using a dispersion machine, and standing for later use.
(2) Preparation of protective film for automobile paint surface
Coating acrylic acid pressure-sensitive glue on a PET release film 10 by using a wire rod, drying at 100 ℃ to form an acrylic acid glue layer with the thickness of 30um, and compounding the acrylic acid glue layer with a TPU base film with the thickness of 150 um; then, the coating liquid prepared above is coated on the other side of the TPU-based film by a wire bar, dried and cured for 5min at 90 ℃/120 ℃/150 ℃ in a step-heating manner to obtain a coating layer with a thickness of about 10um, and the PET release film 50 is compounded on the surface of the coating layer, and then the coating layer is put into an oven and cured for 48 hours at 50 ℃, so that the automobile paint surface protective film according to example 7 is obtained, and the performance of the protective film is tested, and the results are shown in table 4.
Example 8
(1) Preparation of self-repairing coating liquid:
and (3) putting the materials into the charging barrel according to the batching table, dispersing for 10min at a high speed of 400rpm by using a dispersion machine, and standing for later use.
(2) Preparation of protective film for automobile paint surface
Coating acrylic acid pressure-sensitive glue on a PET release film 10 by using a wire rod, drying at 100 ℃ to form an acrylic acid glue layer with the thickness of 30um, and compounding the acrylic acid glue layer with a TPU base film with the thickness of 150 um; then, the coating liquid prepared above is coated on the other side of the TPU base film by using a wire bar, and is dried and cured for 5min at 90 ℃/120 ℃/150 ℃ in a step heating manner to obtain a coating layer with the thickness of about 10um, and a PET release film 50 is compounded on the surface of the coating layer, and the coating layer is put into an oven and cured for 48 hours at 50 ℃, so that the automobile paint surface protective film according to the example 8 is obtained, and the performance of the protective film is tested, and the results are shown in table 4.
Example 9
(1) Preparation of self-repairing coating liquid:
and (3) putting the materials into the charging barrel according to the batching table, dispersing for 10min at a high speed of 400rpm by using a dispersion machine, and standing for later use.
(2) Preparation of protective film for automobile paint surface
Coating acrylic acid pressure-sensitive glue on a PET release film 10 by using a wire rod, drying at 100 ℃ to form an acrylic acid glue layer with the thickness of 30um, and compounding the acrylic acid glue layer with a TPU base film with the thickness of 150 um; then, the coating liquid prepared above is coated on the other side of the TPU-based film by a wire bar, dried and cured for 5min at 90 ℃/120 ℃/150 ℃ in a step-heating manner to obtain a coating layer with a thickness of about 10um, and the PET release film 50 is compounded on the surface of the coating layer, and then the coating layer is put into an oven and cured for 48 hours at 50 ℃, so that the automobile paint surface protective film according to example 9 is obtained, and the performance of the protective film is tested, and the results are shown in table 4.
TABLE 4 test data sheet for each application example
The data testing methods in the table are as follows:
1. repairing speed: forcibly scratching the self-repairing coating by using a copper brush, then flushing scratches by using hot water at about 70 ℃, and recording scratch repairing time by using a stopwatch;
2. the anti-fouling performance is as follows: samples of 50mm by 50mm in size were cut out in 9 pieces. The mixture is placed for at least 24 hours under the environment conditions of 15-28 ℃ and 40-80% RH. A red oily marker meeting the specification of A.3.1 in appendix A of JG/T304-2011 is selected, a mark with the area of 20mm multiplied by 20mm is coated on the center of the membrane surface, three groups of three samples are coated, and the three samples are placed for 2 hours under the same environmental conditions for testing. Wiping the sticky marks of a group of samples with lint-free cotton cloth stained with alcohol for 25 times in a reciprocating manner, and observing the state of the samples after wiping;
3. yellowing resistance: 6 samples with the size of 150mm x 70mm are cut, every two samples are oppositely pasted after peeling off a release film to prepare 3 test samples, and the test samples are placed in a xenon lamp aging test box for testing; the experimental conditions are that the lamp tube is 340nm, and the irradiance is 0.93W/m 2 The blackboard temperature is 63 ℃ and the relative humidity is 65%; in the experiment process, the sample rack is always rotated and continuously placed under illumination and intermittent spraying, each experiment period comprises 102min illumination plus 18min illumination and water spraying, and the water spraying temperature is 20 +/-5 ℃; testing for 408h, taking out the sample, and returning to the room temperature; miningMeasuring the reflectance spectrum with a C light source and a measurement condition of 2 DEG, calculating color parameters L, a, b of the sample after the test, and calculating the color difference Delta E before and after the test ab *. The color difference calculation formula is as follows:
in the formula:
ΔL * 、Δa * 、Δb * respectively as the color parameter L of the test specimen * 、a * 、b * Comparing the change difference before the experiment;
from the test results, the automobile paint protective film prepared by the self-repairing coating resin composite material for the automobile paint protective film provided by the invention has excellent self-repairing speed, excellent anti-fouling performance and excellent yellowing resistance, and has good commercial utilization value.
In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (7)
1. The yellowing-resistant self-repairing coating composition is characterized by comprising the following raw materials in parts by weight:
wherein the hydroxyl-terminated polyurethane prepolymer and the branched hydroxyl polyester account for 100 parts by weight;
the hydroxyl-terminated polyurethane prepolymer is synthesized from the following raw materials: a polyether triol; a polyester diol; a reactive wetting and leveling agent; a reactive slip agent; a reactive ultraviolet absorber; an antioxidant; an aliphatic diisocyanate; a second solvent and a second catalyst;
the polyether triol is selected from one or more of polyoxypropylene/oxyethylene copolymer triol and polyoxypropylene triol, and the number average molecular weight of the polyether triol is 1000-10000;
the polyester diol is selected from one or more of polycaprolactone diol, poly neopentyl glycol adipate diol, poly hexanediol adipate diol, poly diethylene glycol adipate diol, poly butanediol neopentyl glycol adipate diol, poly methyl propylene glycol adipate diol and polycarbonate diol, and the number average molecular weight of the polyester polyol is 1000-4000;
the reactive wetting and leveling agent is organic silicon modified polyether polyol;
the reactive antifouling slip agent is selected from one of perfluoropolyether alcohol and perfluoropolyether amide ethyl alcohol;
the reactive ultraviolet absorbent is selected from one or two of benzophenone and benzotriazole ultraviolet absorbents with active hydroxyl;
the aliphatic diisocyanate is selected from one or two of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate;
the antioxidant is selected from one of antioxidant 1010, antioxidant 1076, antioxidant 245 and antioxidant 1135;
the second catalyst is selected from one of organic tin and organic bismuth catalysts;
the second solvent is selected from one or more of ethyl acetate, butyl acetate, dimethyl carbonate, butanone, toluene and xylene;
the branched hydroxyl polyester is selected from one or two of Korsakowo Desmophen670 and Bassfer Sovermol 1052;
the chain extender is selected from one of 1, 4-butanediol, diethylene glycol and neopentyl glycol;
the curing agent is selected from one of basofbasonat HI100, basofbasonat HI 190B/S, isophorone diisocyanate and dicyclohexylmethane diisocyanate;
the first catalyst is selected from one of organic tin and organic bismuth catalysts;
the first solvent is selected from one or more of ethyl acetate, butyl acetate, dimethyl carbonate, butanone, toluene and xylene.
2. The yellowing-resistant self-healing coating composition of claim 1, wherein the polyether triol has a number average molecular weight of 3000-6000;
the organic silicon modified polyether polyol is selected from one of hydroxyl-terminated single-functionality organic silicon modified polyether, hydroxyl-terminated double-functionality organic silicon modified polyether and side hydroxyl double-functionality organic silicon modified polyether.
3. The yellowing-resistant self-healing coating composition of claim 1, wherein the hydroxyl terminated polyurethane prepolymer is prepared by:
1) uniformly mixing polyether triol, polyester diol, a reactive wetting and leveling agent, a reactive slip agent, a reactive ultraviolet absorber, aliphatic isocyanate and an antioxidant in a second solvent at a reaction temperature of 50-60 ℃ to obtain a first reaction mixture;
2) and adding a second catalyst into the first reaction mixture, gradually heating to 85-95 ℃, reacting at normal pressure, and discharging when the NCO content is reduced to zero to obtain the hydroxyl-terminated polyurethane prepolymer.
4. The yellowing-resistant self-healing coating composition according to claim 3, wherein in step 2), after the gradual temperature rise to 85 to 95 ℃ and the atmospheric reaction for 4 to 6 hours, the NCO content is measured every half hour until the NCO content drops to zero.
5. An automobile paint protective film, which is characterized by sequentially comprising a PET release film, a yellowing-resistant self-repairing coating, a TPU base film, an acrylic acid pressure-sensitive adhesive and a PET release film from top to bottom, wherein the yellowing-resistant self-repairing coating is prepared from the yellowing-resistant self-repairing coating composition as claimed in any one of claims 1-4.
6. The preparation method of the protective film for the automobile paint surface is characterized by comprising the following steps of:
s1: dispersing the raw material components of the yellowing-resistant self-repairing coating composition as defined in any one of claims 1 to 4 by a dispersion machine at a high speed of 400-1000rpm for 10min to obtain a self-repairing coating liquid;
s2: coating acrylic acid pressure-sensitive glue on a PET release film, drying at 100 ℃ to form an acrylic acid glue layer, and compounding the acrylic acid glue layer with a TPU base film; and then coating the self-repairing coating liquid on the other side of the TPU base film, drying and curing at 90 ℃/120 ℃/150 ℃ in a step heating mode to obtain a yellowing-resistant self-repairing coating, compounding another PET release film on the surface of the yellowing-resistant self-repairing coating, putting the PET release film into a drying oven, and curing at 50 ℃ to obtain the automobile paint surface protective film.
7. The method of claim 6, wherein the applying the self-healing coating liquid to the TPU base film in step S2 comprises applying the self-healing coating liquid to the TPU base film with a wire bar.
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