CN115011265A - Tearing-resistant color-changing film and preparation method thereof - Google Patents

Tearing-resistant color-changing film and preparation method thereof Download PDF

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Publication number
CN115011265A
CN115011265A CN202210717804.8A CN202210717804A CN115011265A CN 115011265 A CN115011265 A CN 115011265A CN 202210717804 A CN202210717804 A CN 202210717804A CN 115011265 A CN115011265 A CN 115011265A
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resistant
tearing
layer
terminated polyurethane
hydroxyl
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CN115011265B (en
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周永南
刘波
徐燕峰
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Great Rich Technology Co Ltd
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Great Rich Technology Co Ltd
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Priority to PCT/CN2022/130614 priority patent/WO2023245958A1/en
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Abstract

The invention discloses a tearing-resistant color-changing film which comprises a substrate layer, wherein the substrate layer comprises a colored film layer, a pressure-sensitive adhesive layer is arranged on the first surface of the substrate layer, a tearing-resistant repairing layer prepared by curing a tearing-resistant repairing coating liquid is arranged on the second surface of the substrate layer, and the tearing-resistant repairing coating liquid mainly comprises a main agent resin, a curing agent, an initiator and a solvent; the main agent resin comprises hydroxyl-terminated polyurethane and sulfhydryl-terminated polyurethane; the polymeric monomers of the hydroxyl terminated polyurethane and/or the mercapto terminated polyurethane include polyether polyols. The tearing-resistant repair coating liquid comprises main agent resin hydroxyl-terminated polyurethane and mercapto-terminated polyurethane, wherein the hydroxyl-terminated polyurethane and the mercapto-terminated polyurethane are compounded and cured to form a tearing-resistant repair layer with a cross-linked structure, the self-repair capability is strong, the extensibility is excellent, the toughness is matched with the base material layer, fine wiredrawing is not easy to occur, and the tearing-resistant performance of the color-changing film is improved; the flexibility of the repair layer is further improved by polyether polyol polymerization monomers.

Description

Tearing-resistant color-changing film and preparation method thereof
Technical Field
The invention relates to the field of automobile films, in particular to a tearing-resistant color-changing film and a preparation method thereof.
Background
The common car body color changing film is a PVC (polyvinyl chloride) material and a Polyurethane (PU) material color changing film, the surface of the PVC color changing film has poor high temperature resistance and ageing resistance, and the aging of PVC is easy to accelerate after the PVC color changing film is blown by wind and sun for a long time in an outdoor environment. Compared with a PVC color-changing film, the toughness of the polyurethane color-changing film is enhanced, but the polyurethane color-changing film still has poor weather resistance, poor alkali corrosion resistance and poor anti-fouling performance, and can gradually become yellow and cannot be repaired.
In the prior art, a patent with publication number CN110218525A discloses a TPU substrate invisible car cover protective film, which comprises a protective layer, a substrate layer and a release layer, wherein the protective layer and the release layer are both made of PET, and the substrate layer is made of a polyester-polyether copolymer system; the surface of the substrate layer is respectively bonded with a lower bonding layer and an upper bonding layer, the lower bonding layer is an aliphatic pressure-sensitive adhesive, and the upper bonding layer is an aliphatic polyurethane or urethane-acrylic-based surface coating. Also provides a manufacturing process of the invisible car cover protective film of the TPU substrate, which comprises the following steps: (1) forming a TPU base material layer, (2) carrying out base material layer pretreatment, (3) forming a lower bonding layer, (4) carrying out film transfer, (5) forming an upper bonding layer, and (6) forming a protective layer.
The defects of the prior art are as follows:
the phenomenon of poor appearance such as orange peel, bubbles and the like is easily generated in the preparation process of the protective film for the automobile clothes; the phenomenon of tensile coating fracture is easy to occur in large-amplitude wrap angle construction, and the coating is difficult to repair after the coating fractures.
Disclosure of Invention
One of the purposes of the invention is to overcome the defects in the prior art and provide a tear-resistant color-changing film, the main agent resin hydroxyl-terminated polyurethane and sulfhydryl-terminated polyurethane are cured to form a repairing layer with a cross-linked structure, and the tear-resistant color-changing film has the properties of strong self-repairing capability, excellent extensibility, tear resistance and the like; the flexibility of the repair layer is further improved by polyether polyol polymerization monomers.
In order to realize the process effect, the technical scheme of the invention is as follows: a tearing-resistant color-changing film comprises a substrate layer, wherein the substrate layer comprises a colored film layer, a pressure-sensitive adhesive layer is arranged on the first surface of the substrate layer, a tearing-resistant repairing layer solidified by a tearing-resistant repairing coating liquid is arranged on the second surface of the substrate layer, and the tearing-resistant repairing coating liquid mainly comprises a main agent resin, a curing agent, an initiator and a solvent; the main agent resin comprises hydroxyl-terminated polyurethane and mercapto-terminated polyurethane; the polymeric monomer of the hydroxyl terminated polyurethane and/or the mercapto terminated polyurethane comprises polyether polyol.
In order to optimize the composition of the main agent resin, the tear-resistant repair layer achieves excellent self-repair performance and a cross-linking structure between the main agent resins, the mechanical performance of the compounded main agent resins is improved, the toughness is matched with the substrate layer, and fine wiredrawing is not easy to occur, the preferable technical scheme is that the mass ratio of the hydroxyl-terminated polyurethane to the mercapto-terminated polyurethane is 1: (4-10).
In order to optimize the tear-resistant repair coating liquid, the preferable technical scheme is that the tear-resistant repair coating liquid mainly comprises, by mass, 100 parts of a main agent resin, 4-8 parts of a curing agent, 1-3 parts of an initiator and 130-230 parts of a solvent.
In order to optimize a cohesive structure of hydroxyl-terminated polyurethane, improve the flexibility, aging resistance and mechanical properties of a tear-resistant repair layer and effectively solve the problem that fracture is difficult to repair when the tear-resistant repair layer and a base material layer are compounded and then used, the preferred technical scheme is that the hydroxyl-terminated polyurethane is prepared by catalytically polymerizing first polyisocyanate and first polyether polyol to obtain a first polyurethane prepolymer, crosslinking the first polyurethane prepolymer with a first chain extender to obtain a polyurethane polymer, and adding dihydric alcohol for end capping; the first polyether polyol comprises hydroxyl-terminated unsaturated polyether and saturated polyether polyol, and the molar ratio of the hydroxyl-terminated unsaturated polyether to the saturated polyether polyol is 1: (1-6).
In order to optimize the cohesive structure of the mercapto-terminated polyurethane, improve the flexibility, the repairing performance and the mechanical performance of the tear-resistant repairing layer and effectively solve the problem that the fracture is difficult to repair when the tear-resistant repairing layer is compounded with a base material layer after being used, the preferable technical scheme is that the mercapto-terminated polyurethane is prepared by catalyzing and polymerizing second polyisocyanate and second polyether polyol to obtain a second polyurethane prepolymer and crosslinking the second polyurethane prepolymer with a second chain extender; the second polyether polyol comprises polyether triol and polyether diol, and the molar ratio of the polyether triol to the polyether diol is 1: (1-2).
In order to improve the self-repairing performance, the corrosion resistance and the mechanical performance of the tear-resistant repairing layer, optimize the cohesive cross-linking structure and prolong the service life of the color-changing film, the preferable technical scheme is that the first chain extender is 1, 4-butanediol and/or nanocrystalline cellulose, and the mass of the first chain extender is 1.6-3.6% of the total mass of the first polyurethane prepolymer. The nanocrystalline cellulose can improve the self-repairing performance and the corrosion resistance of the tearing-resistant repairing layer, and optimizes a cross-linking structure in a polyurethane molecule, so that the toughness and the elasticity of the color-changing film are improved.
In order to improve the self-repairing performance of the tear-resistant repairing layer, the preferable technical scheme is that the second chain extender is beta-mercaptoethanol, and the molar ratio of the second chain extender to the second polyisocyanate is (0.9-1.1): 1.
in order to improve the flatness and smoothness of the tear-resistant repair layer and the mechanical properties of the formed repair layer, the preferable technical scheme is that the curing agent is one or more of dimer or trimer of hexamethylene diisocyanate and dimer or trimer of isophorone diisocyanate; the initiator comprises a first initiator and a second initiator, the second initiator is a mixed solution of hydrogen peroxide and sodium iodide, and the first initiator is a peroxy initiator. The second initiator promotes the crosslinking of the mercapto-terminated polyurethane to form a disulfide bond; the first initiator promotes the crosslinking of unsaturated bonds of the hydroxyl-terminated unsaturated polyether of the polymerized monomer in the hydroxyl-terminated polyurethane, further improves the mechanical property of the tear-resistant repair layer, and improves the adhesive force with the substrate layer.
The second purpose of the present invention is to overcome the defects in the prior art, and to provide a method for preparing a tear-resistant color-changing film, comprising the following steps:
s1: respectively preparing hydroxyl-terminated polyurethane and sulfhydryl-terminated polyurethane;
s2: preparing a tearing-resistant repair coating liquid;
s3: preparing a substrate layer
S4: coating the tearing-resistant repair coating liquid on the second surface of the base material layer;
s5: drying and curing;
s6: and (3) adhering a PET protective film to the surface of the cured tearing-resistant repairing layer, and curing to obtain the tearing-resistant color-changing film.
The preferable technical scheme is that the drying and curing temperature of the tearing-resistant repair coating liquid is set to be 60 +/-3 ℃, 80 +/-3 ℃, 100 +/-3 ℃, 110 +/-3 ℃, 120 +/-3 ℃, 110 +/-3 ℃, 100 +/-3 ℃, 90 +/-3 ℃, 80 +/-3 ℃ and 60 +/-3 ℃. The curing temperature is sequentially increased and then decreased, so that in the curing process of the tear-resistant repair layer, the phenomenon that the conduction of energy from outside to inside is not uniform is prevented, the outer layer is cured too fast, the further conduction of the energy to the inside is prevented, the crosslinking of the main agent resin and the volatilization of the solvent are influenced, the effect of the formula between the main agent resins in the tear-resistant repair layer and the crosslinking structure are influenced, and further the mechanical property is negatively influenced. Primary crosslinking of the mercapto-terminated polyurethane at the temperature of 60-80 ℃, and further crosslinking and curing at the temperature of 100-110 ℃; curing and crosslinking reaction of hydroxyl-terminated polyurethane at 100-120 ℃.
In order to further cure and optimize a cross-linking structure of the main agent resin in the tear-resistant repair layer and improve the mechanical property and stability of the tear-resistant repair layer and the base material layer, the preferable technical scheme is that the curing temperature is 50-60 ℃ and the time is 24-72 hours.
The invention has the advantages and beneficial effects that:
the tearing-resistant repair coating liquid comprises main agent resin hydroxyl-terminated polyurethane and mercapto-terminated polyurethane, wherein the hydroxyl-terminated polyurethane and the mercapto-terminated polyurethane are compounded and cured to form a tearing-resistant repair layer with a cross-linked structure, the self-repair capability is strong, the extensibility is excellent, the toughness is matched with the base material layer, fine wiredrawing is not easy to occur, and the tearing-resistant performance of the color-changing film is improved; the flexibility of the repair layer is further improved by polyether polyol polymerization monomers.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Selection of the first polyisocyanate and the second polyisocyanate
Including but not limited to one or more of aliphatic isocyanates and aromatic isocyanates.
Further, the first polyisocyanate and the second polyisocyanate are both aliphatic isocyanates, and the aliphatic isocyanates are one or more of hexamethylene-1, 6-diisocyanate (HDI) and isophorone diisocyanate (IPDI).
Further, the first polyisocyanate and the second polyisocyanate are both isophorone diisocyanate (IPDI). IPDI has two different types of-NCO groups, the groups have different activities, the reaction conditions can be controlled, and polyether polyol selectively reacts with aliphatic primary-NCO to form a-NCO-terminated first polyurethane prepolymer.
A first polyether polyol and a second polyether polyol
The oligomer is an oligomer with molecular end group or/and lateral group containing two or more hydroxyl groups and molecular main chain composed of ether chain.
Selection of the first polyether polyol
Hydroxyl terminated unsaturated polyether and saturated polyether polyol. The mol ratio of the hydroxyl-terminated unsaturated polyether to the saturated polyether polyol is 1: (1-6), and further, the molar ratio of the hydroxyl-terminated unsaturated polyether to the saturated polyether polyol is 1: (3-6).
Saturated polyether polyols
The polyether polyol is saturated polyether polyol with the molecular weight of 1000-1600.
Preparation of hydroxyl-terminated unsaturated polyethers
Adding 1, 3-propylene glycol and potassium hydroxide into a reactor, adding glycidyl methacrylate, and reacting at 75-85 ℃ in a vacuum system to obtain hydroxyl-terminated unsaturated polyether, wherein the molar ratio of the mass of the 1, 3-propylene glycol to the glycidyl methacrylate is 1: (4-5), wherein the addition amount of the potassium hydroxide is 5-6% of the addition amount of the 1, 3-propylene glycol.
Preparation of nanocrystalline cellulose
Mixing microcrystalline cellulose (MCC) and a 25% sulfuric acid aqueous solution according to a mass ratio of 1 (5-6.5), then carrying out hydrolysis treatment in a water bath at 50 ℃ for 2-2.5 h, washing a hydrolysis product to be neutral by using distilled water, drying the hydrolysis product at 68 ℃ until the water content is lower than 1.0%, preparing the acid hydrolyzed microcrystalline cellulose into a suspension with the concentration of 1.2% by using the distilled water, carrying out ultrasonic treatment on the suspension for 500-600 s under the power of 600W by using an ultrasonic cell disruption instrument, and carrying out freeze drying to obtain the nano crystalline cellulose.
Selection of the second polyether polyol
Including but not limited to polyether triols and polyether diols. The polyether triol is polyether triol with the relative molecular weight of 300-800; the polyether diol is polyether diol with the relative molecular weight of 1800-2500.
First chain extender
Including but not limited to one or more of 1, 4-butanediol and nanocrystalline cellulose. Further, the first chain extender is 1, 4-butanediol and nanocrystalline cellulose. Further, the molar ratio of the 1, 4-butanediol to the nanocrystalline cellulose is (7-11): 1.
catalyst and process for preparing same
Including but not limited to tertiary amines, metal compounds, and organic phosphorus. Further, the catalyst is an organic tin compound. Further, the catalyst for the first polyurethane prepolymer and the second polyurethane prepolymer is dibutyltin dilaurate (DBTDL).
Preparation of hydroxyl-terminated polyurethanes
In N 2 In a reaction container under protection, dissolving saturated polyether glycol and IPDI in acetone, dropwise adding 0.3-0.6 wt% of DBTDL, and filling at 70-75 DEG CStirring and reacting for 2-4 h, adding hydroxyl unsaturated polyether, stirring until the content of residual-NCO in the solution is lower than 0.5wt%, obtaining a first polyurethane prepolymer, adding chain extender 1, 4-butanediol and nanocrystalline cellulose, wherein the content of the residual-NCO is 1.6-3.6% of the total mass of the first polyurethane prepolymer, dropwise adding 0.3-0.6 wt% of DBTDL, reacting for 2-4 h, adding 7-10 wt% of glycol, and reacting for 1.5-2 h at 75-80 ℃ to obtain hydroxyl terminated polyurethane. The molar ratio of IPDI to the first polyether polyol (0.4-0.5): (0.6-0.5).
Preparation of mercapto-terminated polyurethanes
In N 2 And (2) mixing polyether triol, polyether diol and IPDI in a protected reaction container, dissolving in ethyl acetate, dropwise adding 0.3-0.6 wt% of DBTDL, fully stirring at 65-70 ℃ for reacting for 2-4 h to obtain a second polyurethane prepolymer, adding a chain extender beta-mercaptoethanol, dropwise adding 0.3-0.6 wt% of DBTDL, and carrying out heat preservation reaction for 6-8 h to obtain the mercapto-terminated polyurethane. The mole ratio of the IPDI to the second polyether polyol is (4-6): 1, the molar ratio of the chain extender beta-mercaptoethanol to the IPDI is (0.9-1.1): 1.
solvent(s)
Including but not limited to one or more of butanone, toluene, isopropanol. Further, the solvent is butanone, toluene and isopropanol.
Initiator
The initiator comprises a first initiator and a second initiator, wherein the second initiator is a mixture of 30-40% of hydrogen peroxide and 1-3 mol% of sodium iodide solution; the first initiator includes, but is not limited to, peroxy and azo types. Further, the first initiator is a peroxy initiator. The peroxy initiator is one or more of benzoyl peroxide, benzoyl t-butyl peroxide and methyl ethyl ketone peroxide, and further, the first initiator is dibenzoyl peroxide (BPO). The molar ratio of the second initiator to the chain extender beta-mercaptoethanol is (1-1.5): 1. the mass of the first initiator is 2-4 wt% of the total mass of the hydroxyl-terminated polyurethane.
Tear-resistant repair coating liquid
The mass ratio of hydroxyl-terminated polyurethane to mercapto-terminated polyurethane is 1: (4-10). Further, the mass ratio of the hydroxyl-terminated polyurethane to the mercapto-terminated polyurethane is 1: (5-9).
Structure of substrate layer
Including first substrate layer and second substrate layer, first substrate layer and second substrate layer are one or more in PVC, TPU and PU and make, are provided with between first substrate layer and the second substrate layer and paste the layer, paste the layer and paste the layer for coloured.
Tearing-resistant color-changing film
The color-changing film core layer comprises a PET protective film, a tearing-resistant repairing layer, a first base material layer, a pasting layer, a second base material layer, a pressure-sensitive adhesive layer and a release film which are sequentially stacked from outside to inside, wherein the tearing-resistant repairing layer, the first base material layer, the pasting layer, the second base material layer and the pressure-sensitive adhesive layer form the color-changing film core layer.
The thickness of the PET protective film is 36-50 mu m, the thickness of the tear-resistant repair layer is 8-10 mu m, the thickness of the first base material layer is 50-80 mu m, the thickness of the adhesive layer is 10-25 mu m, the thickness of the second base material layer is 50-80 mu m, the thickness of the pressure-sensitive adhesive layer is 20-30 mu m, and the thickness of the release film is 50-200 mu m.
Type of the raw materials
Saturated polyether polyol Dow VORANOL 1000 LM;
polyether triol, arkema, france TO 350;
polyether glycol Dow VORANOL223-060 LM;
microcrystalline cellulose (MCC) analytical grade (average particle size of 60-90 μm), Beijing, China chemical Co., Ltd.;
curing agent basf HI-190;
curing agent scientific N3390.
Example 1
Resistant tearing change look membrane is drawn from outer to inner including PET protection film, resistant tearing restoration layer, first substrate layer, pasting layer, second substrate layer, pressure sensitive adhesive layer and the type membrane that stacks gradually.
Preparation of hydroxyl-terminated unsaturated polyether: adding 1, 3-propylene glycol and potassium hydroxide into a reactor, adding glycidyl methacrylate, and reacting at 80 ℃ in a vacuum system to obtain hydroxyl-terminated unsaturated polyether, wherein the mass of the 1, 3-propylene glycol and the molar ratio of the glycidyl methacrylate are 1: 4.2, the addition amount of the potassium hydroxide is 5.4 percent of the addition amount of the 1, 3-propylene glycol.
Preparing nano crystalline cellulose: mixing microcrystalline cellulose (MCC) and 25% sulfuric acid aqueous solution according to the mass ratio of 1:6, then carrying out hydrolysis treatment in a water bath at 50 ℃ for 2h, washing a hydrolysate to be neutral by using distilled water, drying at 68 ℃ until the water content is lower than 1.0%, preparing the acid hydrolyzed microcrystalline cellulose into 1.2% suspension by using the distilled water, carrying out ultrasonic treatment on the suspension for 540s under the power of 600W by using an ultrasonic cell disruption instrument, and carrying out freeze drying to obtain the nano crystalline cellulose.
S1: respectively preparing hydroxyl-terminated polyurethane and sulfhydryl-terminated polyurethane;
preparation of hydroxyl-terminated polyurethane: in N 2 In a reaction container under protection, saturated polyether polyols VORANOL 1000LM and IPDI are dissolved in acetone, 0.5wt% of DBTDL is dripped, the mixture is fully stirred and reacted for 3.5h at 70 ℃, self-made hydroxyl-terminated unsaturated polyether is added and stirred until the content of the residual-NCO in the solution is lower than 0.5wt% to obtain a first polyurethane prepolymer, chain extenders 1, 4-butanediol and nanocrystalline cellulose are added, the content of the residual-NCO in the solution is 3.2% of the total mass of the first polyurethane prepolymer, 0.5wt% of DBTDL is dripped and reacted for 3.5h under heat preservation, 8wt% of glycol is added and reacted for 2h at 75 ℃, and hydroxyl-terminated polyurethane is obtained. The molar ratio of the 1, 4-butanediol to the nanocrystalline cellulose is 9: 1; molar ratio of IPDI to first polyether polyol 4: 6; the mol ratio of the hydroxyl-terminated unsaturated polyether to the saturated polyether polyol VORANOL 1000LM in the first polyether polyol is 1: 5.
preparation of mercapto-terminated polyurethane: in N 2 In a reaction container under protection, polyether triol TO350, polyether diol VORANOL223-060LM and IPDI are mixed and dissolved in ethyl acetate, 0.5wt% of DBTDL is dripped, the mixture is fully stirred and reacts for 3.5 hours at 65 ℃ TO obtain a second polyurethane prepolymer, chain extender beta-mercaptoethanol is added, 0.5wt% of DBTDL is dripped, and the mixture is subjected TO heat preservation reaction for 6 hours TO obtain the mercapto-terminated polyurethane. The molar ratio of IPDI to the second polyether polyol is 5: 1; the molar ratio of the chain extender beta-mercaptoethanol to the IPDI is 1: 1; the molar ratio of the polyether triol to the polyether diol in the second polyether polyol is 1: 1.6.
s2: preparing a tearing-resistant repair coating liquid;
the main components of the tearing-resistant repair coating liquid comprise 100 parts of main agent resin, 6 parts of curing agent, 2.8 parts of initiator and 150 parts of solvent by mass;
the mass ratio of hydroxyl-terminated polyurethane to mercapto-terminated polyurethane in the main agent resin is 1: 8;
the curing agent is Basff HI-190;
the initiator comprises a first initiator and a second initiator, the second initiator is a mixture of 35% of hydrogen peroxide and 2mol% of sodium iodide solution, and the molar ratio of the second initiator to the chain extender beta-mercaptoethanol is 1.2: 1. the first initiator is dibenzoyl peroxide (BPO), and the mass of the first initiator is 3wt% of the total mass of the hydroxyl-terminated polyurethane.
The preparation method of the tearing-resistant color-changing film comprises the following steps:
s3: preparing a substrate layer;
s4: coating the tearing-resistant repair coating liquid on the second surface of the base material layer;
s5: drying and curing; the drying and curing temperatures of the tearing-resistant repair coating liquid are set to be 60 ℃, 80 ℃, 100 ℃, 110 ℃, 120 ℃, 120 ℃, 110 ℃, 100 ℃, 90 ℃, 80 ℃ and 60 ℃;
s6: and (3) adhering a PET protective film to the surface of the cured tearing-resistant repair layer, and curing at 55 ℃ for 36 h.
The total film thickness of the color changing film is 389 mu m, the layer thickness of the PET protective film is 40 mu m, the layer thickness of the tear-resistant repair layer is 9 mu m, the layer thickness of the first base material layer is 60 mu m, the layer thickness of the adhesive layer is 25 mu m, the layer thickness of the second base material layer is 80 mu m, the layer thickness of the pressure-sensitive adhesive layer is 25 mu m, and the layer thickness of the release film is 150 mu m.
Example 2
Example 2 is based on example 1 with the difference that the mass ratio of hydroxyl-terminated polyurethane to mercapto-terminated polyurethane in the base resin, on a volatile free basis, is 1: 10.
example 3
Example 3 is based on example 1 except that the mass ratio of hydroxyl-terminated polyurethane to mercapto-terminated polyurethane in the main agent resin is 1: 4.
example 4
Example 4 is based on example 1, except that the mass ratio of hydroxyl-terminated polyurethane to mercapto-terminated polyurethane in the base resin, on a nonvolatile basis, is 1: 1.
example 5
Example 5 is based on example 1 with the difference that the first polyether polyol comprises only saturated polyether polyol to react to give the first polyurethane prepolymer, which is chain extended to give the hydroxyl terminated polyurethane.
Example 6
Example 6 is based on example 1 except that the second polyether polyol comprises only polyether diol reacted to give the second polyurethane prepolymer and chain extended to give the mercapto-terminated polyurethane.
Example 7
Example 7 is based on example 1 with the difference that the first chain extender is only 1, 4-butanediol involved in the chain extension to give a hydroxyl terminated polyurethane.
Example 8
Example 8 is based on example 1, except that the surface of the tear-resistant repair layer cured in S6 was laminated with a PET protective film and was not cured.
Comparative example 1
Comparative example 1 is based on example 1 with the difference that the main resin is only hydroxyl terminated polyurethane, the curing agent and the second initiator BPO are added, the other components are unchanged and the production process conditions are unchanged.
Comparative example 2
Comparative example 2 is based on example 1 with the difference that the main agent resin is only mercapto-terminated polyurethane, the first initiator is added, the other components are unchanged, and the production process conditions are unchanged.
Comparative example 3
Comparative example 3 is based on example 1 except that the second surface of the substrate layer is not coated with the tear-resistant repair coating liquid.
Performance testing of the core layer of the color-changing film
1. Elongation at break and tensile strength: according to the standards GB/T1040.1 and GB/T1040.3-2006.
2. Scratch resistance: according to the standard GB/T17675-2013, the measurement method, load 5.0N, scribe a full circle test.
3. Puncture resistance: according to standard GB/T21302-2007.
4. Wear resistance: according to the standard GB/T2410, the determination method comprises the following steps: the grinding head is a cylindrical fine or semi-fine grinding felt with the density of 0.52 +/-0.052 g/cm 2 Thickness 10 + -1 mm, diameter 14.5mm + -0.5 mm, vertical friction test. The frequency is 60r/min +/-6 r/min, the stroke is not less than 100mm, the vertical acting force of the grinding head is 10N, the reciprocating friction is carried out for 500 strokes, and after the friction experiment is finished, the haze test is carried out for 96 h.
5. Surface scratch repairability: according to the standard GB/T2410, the determination method comprises the following steps: performing reciprocating test according to the wear resistance, immediately performing haze measurement after the test (H1), then putting the sample into an oven with the temperature of 60 +/-2 ℃ for heat preservation for 120 +/-5 min, taking out the sample, recovering to the room temperature, and performing the haze measurement again (H2); the haze change of the two measurements before and after the calculation was calculated, and the haze recovery rate R = (H1-H2)/H2 × 100% was calculated, and the test result was represented by the average value of the haze recovery rates of the three test specimens and remained to one decimal point.
6. Resistance to impact by crushed stones: the determination method comprises the following steps: a black paint steel plate is used as a substrate, the thickness of the steel plate is 1mm, the thickness of a paint layer is about 0.05 mm, and the size is 230 mm multiplied by 180 mm; the thickness of the aluminum foil is 0.015 mm, and the size is 160mm multiplied by 160 mm; the core layer of the color-changing film is cut out and has the size of 200 mm multiplied by 170 mm. Wet mode system appearance, paste the aluminium foil on black lacquer steel sheet earlier, paste the change look membrane core layer that will cut again on the black lacquer steel sheet that covers there is the aluminium foil, at the temperature: 23 ± 2 ℃, relative humidity: the sample number is 3 pieces, and the sample is kept for at least 72 hours under the condition of 50% + -5%. The distance between a gravel emission opening of the gravel impact resistance test device and the sample is 349 mm, and the distance between a compressed air nozzle opening and the sample is 552 mm. The volume of the gravel storage box is 473 ml, and gravel for washing the pavement with water with the grain diameter of 9.5-16 m is filled in the gravel storage box. The pressure of the compressed air can reach (480 +/-20) kPa, the air pressure is kept for 10 s, the sample is taken off after the experiment is finished, the color-changing film core layer with the center area of 102 mm multiplied by 102 mm and the aluminum foil on the black paint plate are visually checked for damage, and the damage size and the quantity are recorded. The damage number is classified into 0-10 grades, and the 0 grade damage number is more than 250; the number of 1-level damages is 150-250; the number of 2-stage damages is 100-149; the number of 3-grade damages is 75-99; the number of 4-level damages is 50-74; the number of 5-stage damages is 25-49; the number of 6-stage damages is 10-24; the number of 7-grade damages is 5-9; the number of 8-stage damages is 2-4; the number of 9-level breakages is 1; the number of 10-stage breakages is 0.
7. Tear strength: according to the standard GB/T529-.
The test results of the examples and comparative examples are as follows:
Figure 117138DEST_PATH_IMAGE001
in field construction (car body), NG means that the large wrap angle coating is not repairable.
Scratch resistance: OK indicates that the surface has no whole circle of continuous scratches or obvious breakage phenomenon;
the excellent product meets the performance requirements: the fracture productivity is more than or equal to 430 percent; the tensile strength is more than or equal to 30 Mpa, and the tearing strength is more than or equal to 45 KN/m; puncture resistance: not less than 150N (OK); wear resistance: the haze change of the sample before and after friction is less than or equal to 1.2 percent (OK); the haze recovery rate of the surface scratch is more than or equal to 80 percent. The damage quantity of the aluminum foil surface of the base plate in the impact area is not more than 50, the damage size is not more than 1mm, and meanwhile, a paint film does not have penetrating damage marks.
Performance requirements met by industry standard products: the fracture productivity is more than or equal to 150 percent; the tensile strength is more than or equal to 15 Mpa, and the tearing strength is more than or equal to 40 KN/m; puncture resistance: 130N (OK), < 130N (NG) ≧ 130N (OK); wear resistance: the haze change of the sample before and after friction is less than or equal to 1.5 percent (OK) and more than 1.5 percent (NG); the haze recovery rate of the surface scratch is more than or equal to 15 percent; the damage quantity of the aluminum foil surface of the base plate in the impact area is not more than 74, the damage size is not more than 3mm, and meanwhile, a paint film has no penetrating damage mark.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.

Claims (11)

1. A tearing-resistant color-changing film comprises a substrate layer, wherein the substrate layer comprises a colored film layer, a pressure-sensitive adhesive layer is arranged on the first surface of the substrate layer, and the tearing-resistant color-changing film is characterized in that a tearing-resistant repairing layer obtained by curing tearing-resistant repairing coating liquid is arranged on the second surface of the substrate layer, and the tearing-resistant repairing coating liquid mainly comprises a main agent resin, a curing agent, an initiator and a solvent;
the main agent resin comprises hydroxyl-terminated polyurethane and mercapto-terminated polyurethane;
the polymeric monomer of the hydroxyl terminated polyurethane and/or the mercapto terminated polyurethane comprises polyether polyol.
2. The tear-resistant color changing film of claim 1, wherein the hydroxyl-terminated polyurethane and the mercapto-terminated polyurethane are present in a mass ratio of 1: (4-10).
3. The tear-resistant color-changing film according to claim 1 or 2, wherein the tear-resistant repair coating liquid mainly comprises, by mass, 100 parts of a main agent resin, 4-8 parts of a curing agent, 1-3 parts of an initiator, and 130-230 parts of a solvent.
4. The tear-resistant color-changing film as claimed in claim 1 or 2, wherein the hydroxyl-terminated polyurethane is prepared by catalytically polymerizing first polyisocyanate and first polyether polyol to obtain a first polyurethane prepolymer, crosslinking the first polyurethane prepolymer with a first chain extender to obtain a polyurethane polymer, and adding diol to terminate; the first polyether polyol comprises hydroxyl-terminated unsaturated polyether and saturated polyether polyol, and the molar ratio of the hydroxyl-terminated unsaturated polyether to the saturated polyether polyol is 1: (1-6).
5. The tear-resistant color-changing film according to claim 1 or 2, wherein the mercapto-terminated polyurethane is prepared by catalytically polymerizing second polyisocyanate and second polyether polyol to obtain a second polyurethane prepolymer, and crosslinking the second polyurethane prepolymer with a second chain extender; the second polyether polyol comprises polyether triol and polyether diol, and the molar ratio of the polyether triol to the polyether diol is 1: (1-2).
6. The tear-resistant color-changing film according to claim 4, wherein the first chain extender is 1, 4-butanediol and/or nanocrystalline cellulose, and the mass of the first chain extender is 1.6-3.6% of the total mass of the first polyurethane prepolymer.
7. The tear-resistant color-changing film according to claim 5, wherein the second chain extender is β -mercaptoethanol, and the molar ratio of the second chain extender to the second polyisocyanate is (0.9-1.1): 1.
8. the tear-resistant color changing film of claim 1 or 2, wherein the curing agent is one or more of a dimer or trimer of hexamethylene diisocyanate, a dimer or trimer of isophorone diisocyanate; the initiator comprises a first initiator and a second initiator, the second initiator is a mixed solution of hydrogen peroxide and sodium iodide, and the first initiator is a peroxy initiator.
9. A preparation method of a tearing-resistant color-changing film is characterized by comprising the following steps:
s1: respectively preparing hydroxyl-terminated polyurethane and sulfhydryl-terminated polyurethane;
s2: preparing a tearing-resistant repair coating liquid;
s3: preparing a substrate layer
S4: coating the tearing-resistant repair coating liquid on the second surface of the base material layer;
s5: drying and curing;
s6: and (3) adhering a PET protective film to the surface of the cured tearing-resistant repair layer, and curing to obtain the tearing-resistant color-changing film as claimed in claims 1-8.
10. The tear-resistant color-changing film according to claim 9, wherein the drying curing temperature of the tear-resistant repair coating liquid is set to 60 ± 3 ℃, 80 ± 3 ℃, 100 ± 3 ℃, 110 ± 3 ℃, 120 ± 3 ℃, 120 ± 3 ℃, 120 ± 3 ℃, 110 ± 3 ℃, 100 ± 3 ℃, 90 ± 3 ℃, 80 ± 3 ℃, 60 ± 3 ℃.
11. The tear-resistant color-changing film according to claim 9, wherein the curing temperature is 50 to 60 ℃ and the curing time is 24 to 72 hours.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023245958A1 (en) * 2022-06-23 2023-12-28 江阴通利光电科技有限公司 Tear-resistant color-changing film and preparation method therefor

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3446780A (en) * 1965-08-31 1969-05-27 Thiokol Chemical Corp Mercaptan containing polyurethane compositions,process and cured products thereof
US4602071A (en) * 1981-05-29 1986-07-22 Bayer Aktiengesellschaft Process for the production of oligourethanes containing mercapto groups and their use as binders for coating and sealing compositions hardenable by oxidation and as additives for epoxide resins
CN109942773A (en) * 2019-03-18 2019-06-28 四川大学 A kind of selfreparing polyurethane and preparation method thereof of the key of thiourethane containing dynamic
CN110041491A (en) * 2019-04-30 2019-07-23 郑州大学 A kind of high-intensity and high-tenacity selfreparing thermoplastic polyurethane urea elastomer and preparation method
CN110330886A (en) * 2019-07-23 2019-10-15 南昌航空大学 A kind of formula of the light addition self-healing coatings based on sulfydryl alkene
CN110627992A (en) * 2019-10-09 2019-12-31 南昌航空大学 Preparation method of elastomer capable of realizing wide scratch self-repair
WO2020136599A1 (en) * 2018-12-28 2020-07-02 Ptt Global Chemical Public Company Limited A chain extender and a process for preparing a self-healing polyurethane and polyurethane thereof
CN111423602A (en) * 2020-05-27 2020-07-17 青岛科技大学 Self-repairing polyurethane based on hydrogen bond and dynamic disulfide bond, and preparation method and application thereof
CN112239530A (en) * 2020-08-31 2021-01-19 济南大学 Novel method for preparing hydrophobic self-healing super-elastic polyurethane elastomer
CN114163911A (en) * 2021-12-24 2022-03-11 广东亚龙兴新材料有限公司 Self-repairing coating applied to paint surface protective film

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107001557A (en) * 2014-12-15 2017-08-01 三井化学株式会社 Self-repairability polyurethane resin raw material, self-repairability polyurethane resin, self-repairability coating material, self-repairability elastomeric material, the manufacture method of the manufacture method of self-repairability polyurethane resin raw material and self-repairability polyurethane resin
CN212051205U (en) * 2019-12-26 2020-12-01 浦诺菲新材料有限公司 Paint surface protective film
CN113788927A (en) * 2021-10-09 2021-12-14 江苏富琪森新材料有限公司 Self-repairing polyurethane material and preparation method thereof
CN115011265B (en) * 2022-06-23 2023-04-07 江阴通利光电科技有限公司 Tearing-resistant color-changing film and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3446780A (en) * 1965-08-31 1969-05-27 Thiokol Chemical Corp Mercaptan containing polyurethane compositions,process and cured products thereof
US4602071A (en) * 1981-05-29 1986-07-22 Bayer Aktiengesellschaft Process for the production of oligourethanes containing mercapto groups and their use as binders for coating and sealing compositions hardenable by oxidation and as additives for epoxide resins
WO2020136599A1 (en) * 2018-12-28 2020-07-02 Ptt Global Chemical Public Company Limited A chain extender and a process for preparing a self-healing polyurethane and polyurethane thereof
CN109942773A (en) * 2019-03-18 2019-06-28 四川大学 A kind of selfreparing polyurethane and preparation method thereof of the key of thiourethane containing dynamic
CN110041491A (en) * 2019-04-30 2019-07-23 郑州大学 A kind of high-intensity and high-tenacity selfreparing thermoplastic polyurethane urea elastomer and preparation method
CN110330886A (en) * 2019-07-23 2019-10-15 南昌航空大学 A kind of formula of the light addition self-healing coatings based on sulfydryl alkene
CN110627992A (en) * 2019-10-09 2019-12-31 南昌航空大学 Preparation method of elastomer capable of realizing wide scratch self-repair
CN111423602A (en) * 2020-05-27 2020-07-17 青岛科技大学 Self-repairing polyurethane based on hydrogen bond and dynamic disulfide bond, and preparation method and application thereof
CN112239530A (en) * 2020-08-31 2021-01-19 济南大学 Novel method for preparing hydrophobic self-healing super-elastic polyurethane elastomer
CN114163911A (en) * 2021-12-24 2022-03-11 广东亚龙兴新材料有限公司 Self-repairing coating applied to paint surface protective film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023245958A1 (en) * 2022-06-23 2023-12-28 江阴通利光电科技有限公司 Tear-resistant color-changing film and preparation method therefor

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